CN115139672A - Waterproof printing process based on waterborne polyurethane ink - Google Patents

Waterproof printing process based on waterborne polyurethane ink Download PDF

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Publication number
CN115139672A
CN115139672A CN202210833787.4A CN202210833787A CN115139672A CN 115139672 A CN115139672 A CN 115139672A CN 202210833787 A CN202210833787 A CN 202210833787A CN 115139672 A CN115139672 A CN 115139672A
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China
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ink
coating liquid
polyurethane
dosage
process based
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CN202210833787.4A
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CN115139672B (en
Inventor
丁鉴
龚骏杰
刘海晨
朱从刚
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Changzhou Tianfang Printing Co ltd
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Changzhou Tianfang Printing Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/72—Coated paper characterised by the paper substrate
    • D21H19/74—Coated paper characterised by the paper substrate the substrate having an uneven surface, e.g. crêped or corrugated paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D21H19/826—Paper comprising more than one coating superposed two superposed coatings, the first applied being pigmented and the second applied being non-pigmented
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/84—Paper comprising more than one coating on both sides of the substrate
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material

Abstract

The invention discloses a waterproof printing process based on waterborne polyurethane ink, which is mainly applied to surface treatment of corrugated boards and cartons and subsequent ink printing, wherein stearic acid, KH-570 modified silica, polydimethylsiloxane and vinyl polysiloxane are mixed to form a coating solution A during printing, and the coating solution A is coated on the surface of the corrugated boards, so that the waterproof and moistureproof performance of corrugated board preparation can be effectively improved, and the service life of products can be prolonged; but in contrast, the adhesion of the ink is poor when the ink is printed subsequently, which greatly affects the printing effect; therefore, the scheme introduces vinyl polysiloxane into the coating liquid A and also introduces the coating liquid B, and the coating liquid B is used as a transition layer to be connected with the polyurethane ink layer, so that the moisture resistance and the water resistance of the corrugated board are ensured, and meanwhile, the adhesiveness of the polyurethane ink is ensured.

Description

Waterproof printing process based on waterborne polyurethane ink
Technical Field
The invention relates to the technical field of ink printing, in particular to a waterproof printing process based on waterborne polyurethane ink.
Background
The package printing is printing with various packaging materials as carriers, and decorative patterns, patterns or characters are printed on the packages, so that the products are more attractive or descriptive, and the functions of transmitting information and increasing sales volume are achieved.
In the prior art, before printing ink is printed on the surface of a corrugated board, in order to improve the waterproof performance of the corrugated board, the surface of the corrugated board is generally subjected to waterproof treatment, but the adhesive force of the printing ink on the surface of the corrugated board subjected to the waterproof treatment is poor, and if the waterproof treatment process is reduced in order to ensure the ink adhesion effect, the finally processed corrugated board has poor waterproof performance, and the product is easy to absorb moisture, so that inconvenience is brought to practical application.
Based on the situation, the application discloses a waterproof printing process based on waterborne polyurethane ink, so as to solve the technical problem.
Disclosure of Invention
The invention aims to provide a waterproof printing process based on waterborne polyurethane ink, 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 waterproof printing process based on waterborne polyurethane ink comprises the following steps:
(1) Taking stearic acid, KH-570 modified silica and absolute ethyl alcohol, stirring for 20-30 min, adding polydimethylsiloxane and vinyl polysiloxane, and stirring for 2-3h at 50-60 ℃ to obtain coating liquid A;
coating the coating liquid A on the surfaces of two sides of a substrate, drying the substrate in vacuum at the temperature of between 60 and 70 ℃, and then heating the substrate to the temperature of between 110 and 120 ℃ for curing for 30 to 40min to obtain a pretreated substrate;
(2) Mixing the mercapto polyurethane emulsion and the organic silicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B;
taking a pretreated base material, respectively coating the coating liquid B on the surfaces of two sides of the pretreated base material, and carrying out ultraviolet curing for 5-10min to obtain a base material to be printed;
(3) Taking the organic silicon modified polyurethane emulsion, color paste, isopropanol, a photoinitiator and deionized water, and uniformly stirring to obtain polyurethane ink;
taking a substrate to be printed, printing polyurethane ink on the surface of the substrate, curing the substrate for 5 to 10min by ultraviolet light, and drying the substrate at 60 ℃ to obtain a finished product.
According to an optimized scheme, in the step (3), the polyurethane ink comprises the following components in percentage by weight: 60-70 parts of organic silicon modified polyurethane emulsion, 10-12 parts of color paste, 10-12 parts of isopropanol, 30-40 parts of deionized water and 2-3 parts of photoinitiator.
According to an optimized scheme, the preparation method of the mercapto polyurethane emulsion comprises the following steps: taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyltin dilaurate, heating to 70-75 ℃, stirring for reacting for 4-5 h, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, continuing to perform heat preservation reaction for 4-5 h, adding trimethylolpropane tris (2-mercaptoacetate), cooling to 40-50 ℃, preserving heat for 2-3h to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain the mercapto polyurethane emulsion.
According to an optimized scheme, the preparation steps of the organosilicon modified polyurethane emulsion are as follows: taking polyether polyol, polydimethylsiloxane and vinyl polysiloxane, mixing, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, stirring for 20-30 min at 75-80 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, reacting for 2-3h, cooling to 45-50 ℃, neutralizing for 10-15 min with triethylamine, adding deionized water, emulsifying and dispersing for 20-30 min, and obtaining the organosilicon modified polyurethane emulsion with the solid content of 35%.
According to an optimized scheme, in the step (1), in the coating liquid B, the mass ratio of the mercapto polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5:2, the dosage of the photoinitiator is 2 to 3 weight percent of the total mass of the system.
According to a more optimized scheme, the single-side coating amount of the coating liquid A is 20-30 g/m 2 (ii) a The molar ratio of the single-side coating dosage of the coating liquid A to the single-side coating dosage of the coating liquid B is (5-6): 1.
in a more optimized scheme, the preparation steps of the vinyl polysiloxane are as follows: mixing phenyl polysiloxane and octamethylcyclotetrasiloxane, adding a catalyst, adding tetramethyldivinyl disiloxane at the temperature of 115-120 ℃, reacting for 2-3 hours, heating to 170-180 ℃, continuing to react for 4-5 hours, and drying in vacuum after the reaction is finished to obtain vinyl polysiloxane.
According to an optimized scheme, the catalyst is tetramethylammonium hydroxide silicon alkoxide, and the mass ratio of the phenyl polysiloxane, the octamethylcyclotetrasiloxane and the tetramethyldivinyl disiloxane is 1:200:2, the dosage of the catalyst is 0.2 to 0.3 weight percent of the total mass of the system.
According to an optimized scheme, when the mercapto polyurethane emulsion is prepared, the mass ratio of polyether polyol, isophorone diisocyanate and trimethylolpropane tris (2-mercaptoacetate) is 1.1:1:1.5, the dosage of the dibutyltin dilaurate is 0.4-0.5 wt% of the polyether polyol, and the dosage of the dimethylolpropionic acid is 28-30 wt% of the polyether polyol.
In the scheme, the preparation steps of the KH-570 modified silica are as follows: taking nano silicon dioxide and absolute ethyl alcohol, mixing, performing ultrasonic dispersion for 40-50 min to obtain a silicon dioxide solution, adding a KH-570 solution, stirring for 4-5h at the temperature of 60-65 ℃, and drying at the temperature of 110-120 ℃ to obtain KH-570 modified silicon dioxide; the concentration of the silicon dioxide solution is 18-20 mg/mL, the KH-570 solution is prepared by mixing KH-570, absolute ethyl alcohol and deionized water, the concentration of the KH-570 solution is 2-3 mg/mL, and the volume ratio of the solvent absolute ethyl alcohol to the deionized water is 9:1; the mass ratio of the nano silicon dioxide to the KH-570 is 20:1.
the preparation steps of the phenyl polysiloxane are as follows: mixing toluene and deionized water, adding diphenyl dichlorosilane, reacting for 4-5 h at 40-45 ℃, washing in layers, and drying in vacuum to obtain phenyl polysiloxane; the molar ratio of the diphenyl dichlorosilane to the deionized water is 1:10, wherein the volume ratio of the deionized water to the toluene is 5:2.
the preparation steps of the vinyl polysiloxane are as follows: mixing phenyl polysiloxane and octamethylcyclotetrasiloxane, adding a catalyst, adding tetramethyl divinyl disiloxane at the temperature of 115-120 ℃, reacting for 2-3 hours, heating to 170-180 ℃, continuing to react for 4-5 hours, and performing vacuum drying after the reaction is finished to obtain vinyl polysiloxane. The catalyst is tetramethyl ammonium hydroxide silicon alkoxide, and the mass ratio of the phenyl polysiloxane, the octamethylcyclotetrasiloxane and the tetramethyl divinyl disiloxane is 1:200:2, the dosage of the catalyst is 0.2 to 0.3 weight percent of the total mass of the system.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a waterproof printing process based on waterborne polyurethane ink, which is mainly applied to surface treatment of corrugated boards and cartons and subsequent ink printing, wherein stearic acid, KH-570 modified silica, polydimethylsiloxane and vinyl polysiloxane are mixed to form a coating solution A during printing, and the coating solution A is coated on the surface of the corrugated boards, so that the waterproof and moistureproof performance of corrugated board preparation can be effectively improved, and the service life of products can be prolonged; but in contrast, the ink adhesion is poor when the subsequent ink printing is carried out, which greatly affects the printing effect; therefore, the scheme introduces vinyl polysiloxane into the coating liquid A and also introduces the coating liquid B, and the coating liquid B is used as a transition layer to join the polyurethane ink layer, so that the moisture resistance and the water resistance of the corrugated board are ensured, and meanwhile, the adhesiveness of the polyurethane ink is ensured.
According to the scheme, components such as polyether polyol, polydimethylsiloxane, vinyl polysiloxane and isophorone diisocyanate are subjected to polymerization reaction to form organic silicon modified polyurethane emulsion, and the introduction of organic silicon can effectively improve the water resistance of the polyurethane ink.
Meanwhile, the scheme utilizes the organic silicon modified polyurethane emulsion to prepare the polyurethane ink, the organic silicon modified polyurethane emulsion is doped in the coating liquid B, and the mercapto group in the coating liquid and the vinyl in the ink are utilized to carry out photoreaction, so that the adhesive force of the ink can be effectively increased, the wettability of the polyurethane ink and the transition layer (the coating liquid B) is more excellent, and the adhesive fastness is higher.
Here, it is to be emphasized that: the coating liquid B defines that the mass ratio of the mercapto polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5: 2' and simultaneously defines the dosage of the coating liquid A, B, wherein the molar ratio of the dosage of the coating liquid A to the dosage of the coating liquid B for single-side coating is (5-6): 1", this parameter is defined because: in the scheme, the coating liquid B is used as a transition layer to improve the adhesive force of the printing ink, so that a large amount of sulfydryl still needs to be reserved after the coating liquid B is coated with ultraviolet light for curing to ensure the crosslinking between the coating liquid B and the polyurethane printing ink; meanwhile, in order to improve the compatibility between the printing ink and the transition layer, a small amount of organic silicon modified polyurethane emulsion is doped in the coating liquid B so as to ensure the printing effect.
The scheme discloses a waterproof printing process based on waterborne polyurethane ink, which has reasonable process design and proper component proportion, on one hand, a waterproof layer (coating liquid A) is coated on the surface of a base material (corrugated board or carton) so as to improve the waterproof and moistureproof performance of the product, on the other hand, the printing effect of the polyurethane ink is ensured by the arrangement of a transition layer (coating liquid B), and organic silicon modified polyurethane emulsion is also introduced into the polyurethane ink so as to improve the water resistance of the polyurethane ink; the product prepared by the printing process has excellent moisture-proof and water-resistant performance, clear printing ink printing, good ink adhesiveness 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In this example, the preparation of KH-570 modified silica comprises the steps of: mixing nano silicon dioxide and absolute ethyl alcohol, performing ultrasonic dispersion for 40min to obtain a silicon dioxide solution, adding a KH-570 solution, stirring for 5h at the temperature of 60 ℃, and drying at the temperature of 115 ℃ to obtain KH-570 modified silicon dioxide; the concentration of the silicon dioxide solution is 20mg/mL, the KH-570 solution is prepared by mixing KH-570, absolute ethyl alcohol and deionized water, the concentration of the KH-570 solution is 3mg/mL, and the volume ratio of the solvent absolute ethyl alcohol to the deionized water is 9:1; the mass ratio of the nano silicon dioxide to the KH-570 is 20:1.
the preparation steps of the phenyl polysiloxane are as follows: mixing toluene and deionized water, adding diphenyl dichlorosilane, reacting for 5 hours at 45 ℃, washing in layers, and drying in vacuum to obtain phenyl polysiloxane; the molar ratio of the diphenyl dichlorosilane to the deionized water is 1:10, wherein the volume ratio of the deionized water to the toluene is 5:2.
the preparation steps of the vinyl polysiloxane are as follows: mixing phenyl polysiloxane and octamethylcyclotetrasiloxane, adding a catalyst, adding tetramethyldivinyl disiloxane at 115 ℃, reacting for 3 hours, heating to 175 ℃, continuing to react for 4.5 hours, and performing vacuum drying after the reaction is finished to obtain vinyl polysiloxane. The catalyst is tetramethylammonium hydroxide silicon alkoxide, and the mass ratio of the phenyl polysiloxane, the octamethylcyclotetrasiloxane and the tetramethyldivinyl disiloxane is 1:200:2, the dosage of the catalyst is 0.3wt% of the total mass of the system.
The base material is corrugated board.
Example 1:
a waterproof printing process based on waterborne polyurethane ink comprises the following steps:
(1) Taking stearic acid, KH-570 modified silicon dioxide and absolute ethyl alcohol, stirring for 20min, adding polydimethylsiloxane and vinyl polysiloxane, and stirring for 3h at 50 ℃ to obtain coating liquid A; the weight ratio of the stearic acid, the KH-570 modified silica, the polydimethylsiloxane and the vinyl polysiloxane is 1:2:3:1; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating the coating liquid A on the surfaces of two sides of a base material, drying the base material in vacuum at 60 ℃, and then heating to 110 ℃ for curing for 40min to obtain a pretreated base material; the coating amount of the coating liquid A on one side was 25g/m 2 。
(2) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyltin dilaurate, heating to 70 ℃, stirring for reaction for 5 hours, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, continuing to perform heat preservation reaction for 4 hours, adding trimethylolpropane tris (2-mercaptoacetate), cooling to 40 ℃, and performing heat preservation for 3 hours to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain the mercapto-based polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tris (2-mercaptoacetate) is 1.1:1:1.5, the dosage of the dibutyltin dilaurate is 0.5wt% of the polyether polyol, and the dosage of the dimethylolpropionic acid is 28wt% of the polyether polyol. The weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the dosage of the triethylamine is 5wt% of the polyurethane prepolymer.
(3) Mixing polyether polyol N210, polydimethylsiloxane and vinyl polysiloxane, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, stirring for 30min at 75 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, reacting for 2h, cooling to 45 ℃, neutralizing for 10min with triethylamine, adding deionized water, emulsifying and dispersing for 20min, and obtaining the organosilicon modified polyurethane emulsion with the solid content of 35%.
The molar ratio of the isophorone diisocyanate to the polyether polyol is 1.2; the dosage of the polydimethylsiloxane accounts for 5wt% of the total mass of the system; the amount of the vinyl polysiloxane is 4wt% of the total mass of the system; the using amount of the dibutyltin dilaurate is 0.5wt% of the polyether polyol; the dosage of the dimethylolpropionic acid is 24wt% of the polyether polyol; the weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1.
(4) Mixing the mercapto polyurethane emulsion and the organic silicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the mercapto polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5:2, the dosage of the photoinitiator is 3wt% of the total mass of the system.
Coating the coating liquid B on the surfaces of two sides of the pretreated base material respectively, and curing for 10min by ultraviolet light (400W, 365nm) to obtain a base material to be printed; the mole ratio of the single-side coating dosage of the coating liquid A to the single-side coating dosage of the coating liquid B is 5:1.
(5) Taking 60 parts by mass of organic silicon modified polyurethane emulsion, 10 parts by mass of color paste 131-CN (purchased from Claien chemical Co., ltd.), 10 parts by mass of isopropanol, 3 parts by mass of photoinitiator and 30 parts by mass of deionized water, and uniformly stirring to obtain polyurethane ink;
taking a base material to be printed, printing polyurethane ink on the surface, curing by ultraviolet light (400W, 365nm) for 10min, and drying at 60 ℃ to obtain a finished product.
Example 2:
a waterproof printing process based on waterborne polyurethane ink comprises the following steps:
(1) Taking stearic acid, KH-570 modified silicon dioxide and absolute ethyl alcohol, stirring for 25min, adding polydimethylsiloxane and vinyl polysiloxane, and stirring for 2-3h at 55 ℃ to obtain coating liquid A; the weight ratio of the stearic acid, the KH-570 modified silica, the polydimethylsiloxane and the vinyl polysiloxane is 1:2:3:1; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating the coating liquid A on the surfaces of two sides of a base material, drying the base material in vacuum at 65 ℃, and then heating to 115 ℃ for curing for 35min to obtain a pretreated base material; the coating amount of the coating liquid A on one side was 25g/m 2 。
(2) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyltin dilaurate, heating to 75 ℃, stirring for reacting for 4.5h, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, continuing to perform heat preservation reaction for 4.5h, adding trimethylolpropane tris (2-mercaptoacetate), cooling to 45 ℃, and performing heat preservation for 2.5h to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing deionized water to obtain a mercapto-based polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tris (2-mercaptoacetate) is 1.1:1:1.5, the dosage of the dibutyltin dilaurate is 0.5wt% of the polyether polyol, and the dosage of the dimethylolpropionic acid is 28wt% of the polyether polyol. The weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the dosage of the triethylamine is 5wt% of the polyurethane prepolymer.
(3) Mixing polyether polyol N210, polydimethylsiloxane and vinyl polysiloxane, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, stirring for 25min at 75 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, reacting for 2.5h, cooling to 50 ℃, neutralizing for 15min with triethylamine, adding deionized water, emulsifying and dispersing for 25min to obtain the organosilicon modified polyurethane emulsion with the solid content of 35%.
The molar ratio of the isophorone diisocyanate to the polyether polyol is 1.2; the dosage of the polydimethylsiloxane accounts for 5wt% of the total mass of the system; the dosage of the vinyl polysiloxane is 4wt% of the total mass of the system; the using amount of the dibutyltin dilaurate is 0.5wt% of the polyether polyol; the dosage of the dimethylolpropionic acid is 24wt% of the polyether polyol; the weight ratio of the N-methylpyrrolidone to the dimethylolpropionic acid is 2:1.
(4) Mixing the mercapto polyurethane emulsion and the organic silicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the mercapto polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5:2, the dosage of the photoinitiator is 3wt% of the total mass of the system.
Coating the coating liquid B on the surfaces of two sides of the pretreated base material respectively, and curing for 10min by ultraviolet light (400W, 365nm) to obtain a base material to be printed; the mol ratio of the single-side coating dosage of the coating liquid A to the single-side coating dosage of the coating liquid B is 5:1.
(5) Taking 65 parts by mass of organic silicon modified polyurethane emulsion, 11 parts by mass of color paste 131-CN (purchased from Claien chemical Co., ltd.), 11 parts by mass of isopropanol, 3 parts by mass of photoinitiator and 35 parts by mass of deionized water, and uniformly stirring to obtain polyurethane ink;
taking a base material to be printed, printing polyurethane ink on the surface, curing for 5-10min by ultraviolet light (400W, 365nm), and drying at 60 ℃ to obtain a finished product.
Example 3:
a waterproof printing process based on waterborne polyurethane ink comprises the following steps:
(1) Taking stearic acid, KH-570 modified silicon dioxide and absolute ethyl alcohol, stirring for 30min, adding polydimethylsiloxane and vinyl polysiloxane, and stirring for 2h at 60 ℃ to obtain coating liquid A; the weight ratio of the stearic acid, the KH-570 modified silica, the polydimethylsiloxane and the vinyl polysiloxane is 1:2:3:1; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating the coating liquid A on the surfaces of two sides of a base material, drying at 70 ℃ in vacuum, and then heating to 120 ℃ for curing for 30min to obtain a pretreated base material; the coating amount of the coating liquid A on one side was 25g/m 2 。
(2) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyltin dilaurate, heating to 75 ℃, stirring for reaction for 5 hours, adding a mixed solution of N-methylpyrrolidone and dimethylolpropionic acid, continuously performing heat preservation for reaction for 5 hours, adding trimethylolpropane tris (2-mercaptoacetate), cooling to 50 ℃, and performing heat preservation for 2 hours to obtain a polyurethane prepolymer, adding triethylamine to the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain a mercapto polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tris (2-mercaptoacetate) is 1.1:1:1.5, the dosage of the dibutyltin dilaurate is 0.5wt% of the polyether polyol, and the dosage of the dimethylolpropionic acid is 28wt% of the polyether polyol. The weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the dosage of the triethylamine is 5wt% of the polyurethane prepolymer.
(3) Mixing polyether polyol N210, polydimethylsiloxane and vinyl polysiloxane, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, stirring for 20min at 80 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, reacting for 3h, cooling to 45 ℃, neutralizing for 15min with triethylamine, adding deionized water, emulsifying and dispersing for 30min to obtain the organosilicon modified polyurethane emulsion with the solid content of 35%.
The molar ratio of the isophorone diisocyanate to the polyether polyol is 1.2; the dosage of the polydimethylsiloxane accounts for 5wt% of the total mass of the system; the amount of the vinyl polysiloxane is 4wt% of the total mass of the system; the using amount of the dibutyltin dilaurate is 0.5wt% of the polyether polyol; the dosage of the dimethylolpropionic acid is 24wt% of the polyether polyol; the weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1.
(4) Mixing the mercapto polyurethane emulsion and the organic silicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the mercapto polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5:2, the dosage of the photoinitiator is 3wt% of the total mass of the system.
Coating the coating liquid B on the two side surfaces of the pretreated base material respectively, and curing for 5-10min by ultraviolet light (400W, 365nm) to obtain a base material to be printed; the mol ratio of the single-side coating dosage of the coating liquid A to the single-side coating dosage of the coating liquid B is 5:1.
(5) Taking 70 parts by mass of organic silicon modified polyurethane emulsion, 12 parts by mass of color paste 131-CN (purchased from Claien chemical Co., ltd.), 12 parts by mass of isopropanol, 3 parts by mass of photoinitiator and 40 parts by mass of deionized water, and uniformly stirring to obtain polyurethane ink;
taking a base material to be printed, printing polyurethane ink on the surface, curing for 10min by ultraviolet light (400W, 365nm), and drying at 60 ℃ to obtain a finished product.
Comparative example 1: example 2 was used as a control, and coating solution a was not introduced in comparative example 1, and the remaining steps were not changed.
A waterproof printing process based on waterborne polyurethane ink comprises the following steps:
(1) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyltin dilaurate, heating to 75 ℃, stirring for reacting for 4.5h, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, continuing to perform heat preservation reaction for 4.5h, adding trimethylolpropane tris (2-mercaptoacetate), cooling to 45 ℃, and performing heat preservation for 2.5h to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing deionized water to obtain a mercapto-based polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tris (2-mercaptoacetate) is 1.1:1:1.5, the dosage of the dibutyltin dilaurate is 0.5wt% of the polyether polyol, and the dosage of the dimethylolpropionic acid is 28wt% of the polyether polyol. The weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the dosage of the triethylamine is 5wt% of the polyurethane prepolymer.
(2) Mixing polyether polyol N210, polydimethylsiloxane and vinyl polysiloxane, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, stirring for 25min at 75 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, reacting for 2.5h, cooling to 50 ℃, neutralizing for 15min with triethylamine, adding deionized water, emulsifying and dispersing for 25min to obtain the organosilicon modified polyurethane emulsion with the solid content of 35%.
The molar ratio of the isophorone diisocyanate to the polyether polyol is 1.2; the dosage of the polydimethylsiloxane accounts for 5wt% of the total mass of the system; the dosage of the vinyl polysiloxane is 4wt% of the total mass of the system; the using amount of the dibutyltin dilaurate is 0.5wt% of the polyether polyol; the dosage of the dimethylolpropionic acid is 24wt% of the polyether polyol; the weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1.
(3) Mixing the mercapto polyurethane emulsion and the organic silicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the mercapto polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5:2, the dosage of the photoinitiator is 3wt% of the total mass of the system.
Coating the coating liquid B on the two side surfaces of the base material respectively, and curing by ultraviolet light (400W, 365nm) for 10min to obtain a base material to be printed; the coating amount of coating liquid B on one side was 35g/m 2 。
(4) Taking 65 parts by mass of organic silicon modified polyurethane emulsion, 11 parts by mass of color paste 131-CN (purchased from Claien chemical Co., ltd.), 11 parts by mass of isopropanol, 3 parts by mass of photoinitiator and 35 parts by mass of deionized water, and uniformly stirring to obtain polyurethane ink;
taking a base material to be printed, printing polyurethane ink on the surface, curing by ultraviolet light (400W, 365nm) for 5-10min, and drying at 60 ℃ to obtain a finished product.
Comparative example 2: in comparative example 2, which is a control, no silicone modification was performed in the polyurethane ink, and the remaining steps were unchanged.
A waterproof printing process based on waterborne polyurethane ink comprises the following steps:
(1) Taking stearic acid, KH-570 modified silicon dioxide and absolute ethyl alcohol, stirring for 25min, adding polydimethylsiloxane and vinyl polysiloxane, and stirring for 2-3h at 55 ℃ to obtain coating liquid A; the weight ratio of the stearic acid, the KH-570 modified silica, the polydimethylsiloxane and the vinyl polysiloxane is 1:2:3:1; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating the coating liquid A on the surfaces of two sides of a base material, drying the base material in vacuum at 65 ℃, and then heating to 115 ℃ for curing for 35min to obtain a pretreated base material; the coating amount of the coating liquid A on one side was 25g/m 2 。
(2) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyltin dilaurate, heating to 75 ℃, stirring for reacting for 4.5h, adding a mixed solution of N-methylpyrrolidone and dimethylolpropionic acid, continuously performing heat preservation for reacting for 4.5h, adding trimethylolpropane tris (2-mercaptoacetate), cooling to 45 ℃, and performing heat preservation for 2.5h to obtain a polyurethane prepolymer, adding triethylamine to the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain a mercapto polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tris (2-mercaptoacetate) is 1.1:1:1.5, the dosage of the dibutyltin dilaurate is 0.5wt% of the polyether polyol, and the dosage of the dimethylolpropionic acid is 28wt% of the polyether polyol. The weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the amount of triethylamine is 5wt% of the polyurethane prepolymer.
(3) Taking polyether polyol N210, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, stirring at 75 ℃ for 25min, adding isophorone diisocyanate and dibutyltin dilaurate, reacting for 2.5h, cooling to 50 ℃, neutralizing with triethylamine for 15min, adding deionized water, emulsifying and dispersing for 25min, and obtaining a polyurethane emulsion with the solid content of 35%.
The molar ratio of the isophorone diisocyanate to the polyether polyol is 1.2; the dosage of the dibutyltin dilaurate accounts for 0.5wt% of the polyether polyol; the dosage of the dimethylolpropionic acid is 24wt% of the polyether polyol; the weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1.
(4) Mixing the mercapto polyurethane emulsion and the organic silicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the mercapto polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5:2, the dosage of the photoinitiator is 3wt% of the total mass of the system. The procedure for the silicone-modified polyurethane emulsion was as in example 2.
Coating the coating liquid B on the surfaces of two sides of the pretreated base material respectively, and curing for 10min by ultraviolet light (400W, 365nm) to obtain a base material to be printed; the mol ratio of the single-side coating dosage of the coating liquid A to the single-side coating dosage of the coating liquid B is 5:1.
(5) Taking 65 parts of polyurethane emulsion, 11 parts of color paste 131-CN (purchased from Claien chemical Co., ltd.), 11 parts of isopropanol, 3 parts of photoinitiator and 35 parts of deionized water by mass, and uniformly stirring to obtain polyurethane ink;
taking a base material to be printed, printing polyurethane ink on the surface, curing by ultraviolet light (400W, 365nm) for 5-10min, and drying at 60 ℃ to obtain a finished product.
Comparative example 3: the control group of example 2 is used, and the mercapto-vinyl system is not introduced into the comparative example 3, and the rest steps are not changed.
A waterproof printing process based on waterborne polyurethane ink comprises the following steps:
(1) Taking stearic acid, KH-570 modified silicon dioxide and absolute ethyl alcohol, stirring for 25min, adding polydimethylsiloxane, and stirring for 2-3h at 55 ℃ to obtain coating liquid A; the weight ratio of stearic acid, KH-570 modified silicon dioxide and polydimethylsiloxane is 1:2:3; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating the coating liquid A on the surfaces of two sides of a base material, drying the base material in vacuum at 65 ℃, and then heating to 115 ℃ for curing for 35min to obtain a pretreated base material; the coating amount of the coating liquid A on one side was 25g/m 2 。
(2) Mixing polyether polyol N210 and polydimethylsiloxane, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, stirring for 25min at 75 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, reacting for 2.5h, cooling to 50 ℃, neutralizing for 15min with triethylamine, adding deionized water, emulsifying and dispersing for 25min, and obtaining the organosilicon modified polyurethane emulsion with the solid content of 35%.
The molar ratio of the isophorone diisocyanate to the polyether polyol is 1.2; the dosage of the polydimethylsiloxane accounts for 5wt% of the total mass of the system; the using amount of the dibutyltin dilaurate is 0.5wt% of the polyether polyol; the dosage of the dimethylolpropionic acid is 24wt% of the polyether polyol; the weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1.
(3) Taking 65 parts by mass of organic silicon modified polyurethane emulsion, 11 parts by mass of color paste 131-CN (purchased from Claien chemical Co., ltd.), 11 parts by mass of isopropanol, 3 parts by mass of photoinitiator and 35 parts by mass of deionized water, and uniformly stirring to obtain polyurethane ink;
and (3) printing polyurethane ink on the surface of the pretreated base material, and drying at 60 ℃ to obtain a finished product.
Comparative example 4: comparative example 3 was used as a control, and comparative example 4 was not coated with coating liquid a, and the remaining steps were unchanged.
A waterproof printing process based on waterborne polyurethane ink comprises the following steps:
(1) Mixing polyether polyol N210 and polydimethylsiloxane, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, stirring for 25min at 75 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, reacting for 2.5h, cooling to 50 ℃, neutralizing for 15min with triethylamine, adding deionized water, emulsifying and dispersing for 25min, and obtaining the organosilicon modified polyurethane emulsion with the solid content of 35%.
The molar ratio of the isophorone diisocyanate to the polyether polyol is 1.2; the dosage of the polydimethylsiloxane accounts for 5wt% of the total mass of the system; the using amount of the dibutyltin dilaurate is 0.5wt% of the polyether polyol; the dosage of the dimethylolpropionic acid is 24wt% of the polyether polyol; the weight ratio of the N-methyl pyrrolidone to the dimethylolpropionic acid is 2:1.
(2) Taking 65 parts by mass of organic silicon modified polyurethane emulsion, 11 parts by mass of color paste 131-CN (purchased from Claien chemical Co., ltd.), 11 parts by mass of isopropanol, 3 parts by mass of photoinitiator and 35 parts by mass of deionized water, and uniformly stirring to obtain polyurethane ink;
taking a base material, printing polyurethane ink on the surface of the base material, and drying at 60 ℃ to obtain a finished product.
Detection experiment:
the surface of the printing corrugated boards prepared in the examples 1 to 3 and the comparative examples 1 to 4 was subjected to performance test:
1. cutting the printed corrugated board into samples of 5cm multiplied by 10cm, putting half of the samples into deionized water, soaking for 24h at 25 ℃, taking out after soaking, naturally airing, comparing the ink change conditions before and after soaking, and observing the dyeing degree of water.
2. Detecting the adhesion fastness of the polyurethane ink according to GB/T13217.7-2009, wherein an adhesive tape method is adopted during testing, the adhesive tape is adhered to the surface of a corrugated paperboard, a rolling machine rolls the corrugated paperboard back and forth for 3 times, the corrugated paperboard is placed for 5min, the adhesive tape is rotationally uncovered at the speed of 0.8m/s according to the method disclosed by GB/T7707-2008, and the adhesion fastness is observed and calculated.
3. Cutting the printed corrugated board into samples of 5cm multiplied by 10cm, soaking the samples in deionized water for 24h, taking out the samples, wiping off the surface moisture of the samples, weighing the mass of the samples before and after soaking, and calculating the water absorption of the samples.
Item Change after immersion in water Fastness to adhesion Water absorption rate
Example 1 No color change of ink and no dyeing of water 96％ 5.46％
Example 2 No color change of ink and no dyeing of water 97％ 4.93％
Example 3 No color change of ink and no dyeing of water 97％ 5.17％
Comparative example 1 No color change of ink and no dyeing of water 94％ 11.14％
Comparative example 2 Slight color change of ink and slight dyeing of water 89％ 6.48％
Comparative example 3 Obvious color change of ink and obvious dyeing of water 84％ 7.14％
Comparative example 4 Slight color change of ink and slight dyeing of water 90％ 13.17％
And (4) conclusion: the scheme discloses a waterproof printing process based on waterborne polyurethane ink, which has reasonable process design and proper component proportion, on one hand, a waterproof layer (coating liquid A) is coated on the surface of a base material (corrugated board or carton) so as to improve the waterproof and moistureproof performance of the product, on the other hand, the printing effect of the polyurethane ink is ensured by the arrangement of a transition layer (coating liquid B), and organic silicon modified polyurethane emulsion is also introduced into the polyurethane ink so as to improve the water resistance of the polyurethane ink; the product prepared by the printing process has excellent moisture-proof and water-resistant performance, clear printing ink printing, good ink adhesiveness 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 (9)

1. A waterproof printing process based on waterborne polyurethane ink is characterized in that: the method comprises the following steps:
(1) Taking stearic acid, KH-570 modified silicon dioxide and absolute ethyl alcohol, uniformly stirring, adding polydimethylsiloxane and vinyl polysiloxane, and stirring for 2-3h at 50-60 ℃ to obtain coating liquid A;
coating the coating liquid A on the surfaces of two sides of a substrate, drying the substrate in vacuum at the temperature of between 60 and 70 ℃, and then heating the substrate to the temperature of between 110 and 120 ℃ for curing for 30 to 40min to obtain a pretreated substrate;
(2) Mixing the mercapto polyurethane emulsion and the organic silicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B;
taking a pretreated base material, respectively coating the coating liquid B on the surfaces of two sides of the pretreated base material, and carrying out ultraviolet curing for 5-10min to obtain a base material to be printed;
(3) Taking the organic silicon modified polyurethane emulsion, color paste, isopropanol, photoinitiator and deionized water, and uniformly stirring to obtain polyurethane ink;
taking a substrate to be printed, printing polyurethane ink on the surface of the substrate, curing the substrate for 5 to 10min by ultraviolet light, and drying the substrate at the temperature of between 60 and 70 ℃ to obtain a finished product.
2. The waterproof printing process based on the waterborne polyurethane ink as claimed in claim 1, wherein: in the step (3), the polyurethane ink comprises the following components in percentage by weight: by mass, 60-70 parts of organic silicon modified polyurethane emulsion, 10-12 parts of color paste, 10-12 parts of isopropanol, 30-40 parts of deionized water and 2-3 parts of photoinitiator.
3. The waterproof printing process based on the waterborne polyurethane ink as claimed in claim 1, wherein: in the step (2), the preparation of the mercapto polyurethane emulsion comprises the following steps: taking polyether polyol and isophorone diisocyanate, uniformly mixing, adding dibutyltin dilaurate, heating to 70-75 ℃, stirring for reaction for 4-5 h, adding a mixed solution of N-methylpyrrolidone and dimethylolpropionic acid, continuing to perform heat preservation reaction for 4-5 h, adding trimethylolpropane tris (2-mercaptoacetate), cooling to 40-50 ℃, preserving heat for 2-3h to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing deionized water to obtain a mercapto polyurethane emulsion.
4. The waterproof printing process based on the waterborne polyurethane ink as claimed in claim 1, wherein: the preparation method of the organic silicon modified polyurethane emulsion comprises the following steps: mixing polyether polyol, polydimethylsiloxane and vinyl polysiloxane, adding a mixed solution of N-methyl pyrrolidone and dimethylolpropionic acid, stirring for 20-30 min at 75-80 ℃, adding isophorone diisocyanate and dibutyltin dilaurate, reacting for 2-3h, cooling to 45-50 ℃, neutralizing for 10-15 min with triethylamine, adding deionized water, emulsifying and dispersing for 20-30 min, and obtaining the organosilicon modified polyurethane emulsion with the solid content of 35%.
5. The waterproof printing process based on the waterborne polyurethane ink as claimed in claim 1, wherein: in the step (2), in the coating liquid B, the mass ratio of the mercapto polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5:2, the dosage of the photoinitiator is 2 to 3 weight percent of the total mass of the system.
6. The waterproof printing process based on the waterborne polyurethane ink as claimed in claim 1, wherein: the coating amount of the coating liquid A on one side is 20-30 g/m 2 (ii) a The molar ratio of the single-side coating dosage of the coating liquid A to the single-side coating dosage of the coating liquid B is (5-6): 1.
7. the waterproof printing process based on the waterborne polyurethane ink as claimed in claim 1, wherein: in the step (1), the preparation of the vinyl polysiloxane comprises the following steps: mixing phenyl polysiloxane and octamethylcyclotetrasiloxane, adding a catalyst, adding tetramethyl divinyl disiloxane at the temperature of 115-120 ℃, reacting for 2-3 hours, heating to 170-180 ℃, continuing to react for 4-5 hours, and performing vacuum drying after the reaction is finished to obtain vinyl polysiloxane.
8. The waterproof printing process based on the waterborne polyurethane ink as claimed in claim 7, wherein: the catalyst is tetramethylammonium hydroxide silicon alkoxide, and the mass ratio of the phenyl polysiloxane, the octamethylcyclotetrasiloxane and the tetramethyldivinyl disiloxane is 1:200:2, the dosage of the catalyst is 0.2 to 0.3 weight percent of the total mass of the system.
9. The waterproof printing process based on the waterborne polyurethane ink as claimed in claim 3, wherein: when the mercapto polyurethane emulsion is prepared, the mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tris (2-mercaptoacetate) is 1.1:1:1.5, the dosage of the dibutyltin dilaurate is 0.4-0.5 wt% of the polyether polyol, and the dosage of the dimethylolpropionic acid is 28-30 wt% of the polyether polyol.
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