CN115139672B - Waterproof printing process based on water-based polyurethane ink - Google Patents
Waterproof printing process based on water-based polyurethane ink Download PDFInfo
- Publication number
- CN115139672B CN115139672B CN202210833787.4A CN202210833787A CN115139672B CN 115139672 B CN115139672 B CN 115139672B CN 202210833787 A CN202210833787 A CN 202210833787A CN 115139672 B CN115139672 B CN 115139672B
- Authority
- CN
- China
- Prior art keywords
- coating liquid
- polyurethane
- ink
- water
- polyurethane emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 133
- 239000004814 polyurethane Substances 0.000 title claims abstract description 133
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 101
- 238000000576 coating method Methods 0.000 claims abstract description 101
- -1 KH-570 modified silicon dioxide Chemical class 0.000 claims abstract description 96
- 239000007788 liquid Substances 0.000 claims abstract description 82
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 47
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 37
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 36
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 29
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 29
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 19
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 19
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008117 stearic acid Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims description 72
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 63
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 59
- 229920000570 polyether Polymers 0.000 claims description 59
- 229920005862 polyol Polymers 0.000 claims description 59
- 150000003077 polyols Chemical class 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 44
- 229910021641 deionized water Inorganic materials 0.000 claims description 44
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 33
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 31
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 31
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 31
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 30
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 30
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 28
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 13
- 229940071127 thioglycolate Drugs 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 8
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 2
- 230000007704 transition Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000010186 staining Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 4
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RFMXKZGZSGFZES-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OC(=O)CS.CCC(CO)(CO)CO RFMXKZGZSGFZES-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electromagnetism (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a waterproof printing process based on water-based polyurethane ink, which is mainly applied to surface treatment of corrugated boards and cartons and subsequent ink printing, wherein stearic acid, KH-570 modified silicon dioxide, polydimethylsiloxane and vinyl polysiloxane are mixed to form a coating liquid A during printing, and the coating liquid A is coated on the surface of the corrugated boards, so that the waterproof and moistureproof performances of corrugated preparation can be effectively improved, and the service life of products is prolonged; however, in contrast, when ink printing is performed subsequently, the adhesive force of the ink is poor, which greatly influences the printing effect; therefore, vinyl polysiloxane is introduced into the coating liquid A, meanwhile, the coating liquid B is used as a transition layer to be connected with the polyurethane ink layer, and the adhesiveness of the polyurethane ink is ensured while the moisture and water resistance of the corrugated board is ensured.
Description
Technical Field
The invention relates to the technical field of ink printing, in particular to a waterproof printing process based on water-based polyurethane ink.
Background
The packaging printing is printing with various packaging materials as carriers, and decorative patterns, patterns or characters are printed on the packaging, so that the product is more attractive or more explanatory, the effect of transmitting information and increasing sales is achieved, and the polyurethane printing ink is a common ink choice.
In the prior art, before ink printing is performed 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 ink on the surface of the corrugated board after the waterproof treatment is poor, and if the waterproof treatment process is reduced in order to ensure the ink adhesion effect, the waterproof performance of the corrugated board formed by final processing is poor, the product is easy to absorb moisture, and inconvenience is brought to practical application.
Based on the situation, the application discloses a waterproof printing process based on water-based polyurethane ink, so as to solve the technical problem.
Disclosure of Invention
The invention aims to provide a waterproof printing process based on water-based polyurethane ink, which aims 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 water-based polyurethane ink comprises the following steps:
(1) Taking stearic acid, KH-570 modified silicon dioxide 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 liquid A on the surfaces of two sides of a substrate, vacuum drying at 60-70 ℃, and curing for 30-40 min at 110-120 ℃ to obtain a pretreated substrate;
(2) Mixing the sulfhydryl polyurethane emulsion and the organosilicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B;
coating liquid B on the surfaces of two sides of the pretreated base material respectively, and ultraviolet curing for 5-10min to obtain the base material to be printed;
(3) Taking organic silicon modified polyurethane emulsion, color paste, isopropanol, a photoinitiator and deionized water, and uniformly stirring to obtain polyurethane ink;
and (3) taking a substrate to be printed, printing polyurethane ink on the surface, ultraviolet curing for 5-10min, and drying at 60 ℃ to obtain a finished product.
In a more optimized scheme, in the step (3), the content of each component of the polyurethane ink comprises: 60-70 parts of organosilicon 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.
In an optimized scheme, the preparation steps of the sulfhydryl polyurethane emulsion are as follows: taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyl tin dilaurate, heating to 70-75 ℃, stirring and reacting for 4-5 hours, adding mixed solution of N-methylpyrrolidone and dimethylolpropionic acid, continuously preserving heat and reacting for 4-5 hours, adding trimethylolpropane tri (2-thioglycolate), cooling to 40-50 ℃, preserving heat for 2-3 hours to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain the mercapto polyurethane emulsion.
The preparation method of the organosilicon modified polyurethane emulsion comprises the following steps: mixing polyether polyol, polydimethylsiloxane and vinyl polysiloxane, adding N-methyl pyrrolidone and dimethylol propionic acid mixed solution, 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%.
In the more optimized scheme, in the step (1), in the coating liquid B, the mass ratio of the sulfhydryl polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5:2, the dosage of the photoinitiator is 2-3 wt% of the total mass of the system.
More optimized scheme, the single-sided coating amount of the coating liquid A is 20-30 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The single-side coating dosage mole ratio of the coating liquid A to the coating liquid B is (5-6): 1.
more optimized scheme, the preparation steps of the vinyl polysiloxane are as follows: mixing phenyl polysiloxane and octamethyl cyclotetrasiloxane, adding a catalyst, adding tetramethyl divinyl disiloxane at 115-120 ℃, reacting for 2-3h, heating to 170-180 ℃, continuing to react for 4-5 h, and vacuum drying after the reaction is finished to obtain vinyl polysiloxane.
In a more optimized scheme, the catalyst is tetramethyl ammonium hydroxide silicon alkoxide, and the mass ratio of phenyl polysiloxane, octamethyl cyclotetrasiloxane and 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.
In a more optimized scheme, when the mercapto polyurethane emulsion is prepared, the mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tri (2-mercaptoacetate) is 1.1:1:1.5, the dosage of the dibutyl tin dilaurate is 0.4 to 0.5 weight percent of the polyether polyol, and the dosage of the dimethylolpropionic acid is 28 to 30 weight percent of the polyether polyol.
In the scheme, the preparation steps of KH-570 modified silicon dioxide are as follows: mixing nano silicon dioxide and absolute ethyl alcohol, performing ultrasonic dispersion for 40-50 min to obtain a silicon dioxide solution, adding a KH-570 solution, stirring for 4-5 h at 60-65 ℃, and drying at 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 absolute ethyl alcohol solvent to the deionized water is 9:1, a step of; the mass ratio of the nano silicon dioxide to 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 hours at 40-45 ℃, layering, washing, and vacuum drying to obtain phenyl polysiloxane; the molar ratio of the diphenyl dichlorosilane to the deionized water is 1:10, the volume ratio of deionized water to toluene is 5:2.
the preparation steps of the vinyl polysiloxane are as follows: mixing phenyl polysiloxane and octamethyl cyclotetrasiloxane, adding a catalyst, adding tetramethyl divinyl disiloxane at 115-120 ℃, reacting for 2-3h, heating to 170-180 ℃, continuing to react for 4-5 h, and 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 to the octamethyl cyclotetrasiloxane to 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 water-based polyurethane ink, which is mainly applied to surface treatment of corrugated boards and cartons and subsequent ink printing, wherein stearic acid, KH-570 modified silicon dioxide, polydimethylsiloxane and vinyl polysiloxane are mixed to form a coating liquid A during printing, and the coating liquid A is coated on the surface of the corrugated boards, so that the waterproof and moistureproof performances of corrugated preparation can be effectively improved, and the service life of products is prolonged; however, in contrast, when ink printing is performed subsequently, the adhesive force of the ink is poor, which greatly influences the printing effect; therefore, vinyl polysiloxane is introduced into the coating liquid A, meanwhile, the coating liquid B is used as a transition layer to be connected with the polyurethane ink layer, and the adhesiveness of the polyurethane ink is ensured while the moisture and water resistance of the corrugated board is ensured.
According to the scheme, components such as polyether polyol, polydimethylsiloxane, vinyl polysiloxane and isophorone diisocyanate are polymerized to form organosilicon modified polyurethane emulsion, and the water resistance of polyurethane ink can be effectively improved by introducing organosilicon, so that on the basis of the scheme, the application utilizes the mercapto polyurethane emulsion and the organosilicon modified polyurethane emulsion to mix to form coating liquid B, at the moment, the coating liquid B is coated on the surface of the coating liquid A to serve as a transition layer, ultraviolet light curing is carried out under the action of a photoinitiator, and vinyl in the coating liquid A, mercapto and vinyl in the coating liquid B can be crosslinked with each other, so that the adhesion of the coating liquid B is realized.
Meanwhile, the scheme utilizes the organosilicon modified polyurethane emulsion to prepare polyurethane ink, the organosilicon modified polyurethane emulsion is doped in the coating liquid B, and the adhesive force of the ink can be effectively achieved by utilizing the mercapto group in the coating liquid and the vinyl photoreaction in the ink, so that the wettability of the polyurethane ink and the transition layer (coating liquid B) is more excellent, and the adhesive fastness is higher.
Here, it is emphasized that: the coating liquid B is defined as that the mass ratio of the mercapto polyurethane emulsion to the organosilicon modified polyurethane emulsion is 5:2", and the amount of the coating liquid A, B" the single-side coating amount mole ratio of the coating liquid a and the coating liquid B is (5 to 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 sulfhydryl groups still need to be reserved after the ultraviolet light is coated by the coating liquid B for curing so as to ensure the crosslinking between the coating liquid B and the polyurethane printing ink; meanwhile, in order to improve the compatibility between the ink and the transition layer, a small amount of organosilicon 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 water-based polyurethane ink, which has reasonable process design and proper component proportion, wherein on one hand, a waterproof layer (coating liquid A) is coated on the surface of a base material (corrugated board or paper box) so as to improve the waterproof and dampproof properties of a product, on the other hand, the setting of a transition layer (coating liquid B) is utilized to ensure the printing effect of the polyurethane ink, and an organosilicon 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 resistance and water resistance, clear ink printing, good ink adhesiveness and higher 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, KH-570 modified silica was prepared by 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 60 ℃, and drying at 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 absolute ethyl alcohol solvent to the deionized water is 9:1, a step of; the mass ratio of the nano silicon dioxide to 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 ℃, layering, washing, and vacuum drying to obtain phenyl polysiloxane; the molar ratio of the diphenyl dichlorosilane to the deionized water is 1:10, the volume ratio of deionized water to toluene is 5:2.
the preparation steps of the vinyl polysiloxane are as follows: mixing phenyl polysiloxane and octamethyl cyclotetrasiloxane, adding a catalyst, adding tetramethyl divinyl disiloxane at 115 ℃, reacting for 3 hours, heating to 175 ℃, continuing to react for 4.5 hours, and 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 to the octamethyl cyclotetrasiloxane to the tetramethyl divinyl disiloxane is 1:200:2, the catalyst is used in an amount of 0.3wt% of the total mass of the system.
The base material is corrugated board.
Example 1:
a waterproof printing process based on water-based 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 to the KH-570 modified silicon dioxide to the polydimethylsiloxane to the vinyl polysiloxane is 1:2:3:1, a step of; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating liquid A on the surfaces of two sides of a substrate, vacuum drying at 60 ℃, and curing for 40min at the temperature of 110 ℃ to obtain a pretreated substrate; the single-sided coating amount of the coating liquid A was 25g/m 2 。
(2) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyl tin dilaurate, heating to 70 ℃, stirring and reacting for 5 hours, adding mixed liquid of N-methylpyrrolidone and dimethylolpropionic acid, continuously preserving heat and reacting for 4 hours, adding trimethylolpropane tri (2-thioglycolate), cooling to 40 ℃, preserving heat 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 polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tri (2-thioglycolate) is 1.1:1:1.5, the dibutyl tin dilaurate is used in an amount of 0.5wt% of the polyether polyol, and the dimethylol propionic acid is used in an amount of 28wt% of the polyether polyol. The weight ratio of the N-methylpyrrolidone to the dimethylolpropionic acid is 2:1, a step of; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the amount of the triethylamine is 5 weight percent of the polyurethane prepolymer.
(3) Mixing polyether polyol N210, polydimethylsiloxane and vinyl polysiloxane, adding mixed solution of N-methylpyrrolidone 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 isophorone diisocyanate to polyether polyol is 1.2; the dosage of the polydimethylsiloxane is 5wt% of the total mass of the system; the vinyl polysiloxane amount is 4wt% of the total mass of the system; the dibutyl tin 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 sulfhydryl polyurethane emulsion and the organosilicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the sulfhydryl 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 a coating liquid B on the surfaces of two sides of the pretreated substrate respectively, and curing for 10min by ultraviolet light (400W, 365 nm) to obtain a substrate to be printed; the single-side coating dosage mole ratio of the coating liquid A to the coating liquid B is 5:1.
(5) Taking 60 parts of organosilicon modified polyurethane emulsion, 10 parts of color paste 131-CN (purchased from Kelain chemical industry Co., ltd.), 10 parts of isopropanol, 3 parts of photoinitiator and 30 parts of deionized water by mass, and uniformly stirring to obtain polyurethane ink;
and (3) taking a substrate to be printed, printing polyurethane ink on the surface, curing for 10min by ultraviolet light (400W, 365 nm), and drying at 60 ℃ to obtain a finished product.
Example 2:
a waterproof printing process based on water-based 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 at 55 ℃ for 2-3h to obtain coating liquid A; the weight ratio of the stearic acid to the KH-570 modified silicon dioxide to the polydimethylsiloxane to the vinyl polysiloxane is 1:2:3:1, a step of; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating liquid A on the surfaces of two sides of a substrate, vacuum drying at 65 ℃, and curing for 35min at 115 ℃ to obtain a pretreated substrate; the single-sided coating amount of the coating liquid A was 25g/m 2 。
(2) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyl tin dilaurate, heating to 75 ℃, stirring and reacting for 4.5 hours, adding a mixed solution of N-methylpyrrolidone and dimethylolpropionic acid, continuously preserving heat and reacting for 4.5 hours, adding trimethylolpropane tri (2-thioglycolate), cooling to 45 ℃, preserving heat for 2.5 hours to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain the mercapto polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tri (2-thioglycolate) is 1.1:1:1.5, the dibutyl tin dilaurate is used in an amount of 0.5wt% of the polyether polyol, and the dimethylol propionic acid is used in an amount of 28wt% of the polyether polyol. The weight ratio of the N-methylpyrrolidone to the dimethylolpropionic acid is 2:1, a step of; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the amount of the triethylamine is 5 weight percent of the polyurethane prepolymer.
(3) Mixing polyether polyol N210, polydimethylsiloxane and vinyl polysiloxane, adding mixed solution of N-methylpyrrolidone 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 the organosilicon modified polyurethane emulsion with the solid content of 35%.
The molar ratio of isophorone diisocyanate to polyether polyol is 1.2; the dosage of the polydimethylsiloxane is 5wt% of the total mass of the system; the vinyl polysiloxane amount is 4wt% of the total mass of the system; the dibutyl tin 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 sulfhydryl polyurethane emulsion and the organosilicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the sulfhydryl 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 a coating liquid B on the surfaces of two sides of the pretreated substrate respectively, and curing for 10min by ultraviolet light (400W, 365 nm) to obtain a substrate to be printed; the single-side coating dosage mole ratio of the coating liquid A to the coating liquid B is 5:1.
(5) Taking 65 parts by mass of organosilicon modified polyurethane emulsion, 11 parts by mass of color paste 131-CN (purchased from Coryn 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) taking a substrate to be printed, printing polyurethane ink on the surface, curing for 5-10min by ultraviolet light (400W, 365 nm), and drying at 60 ℃ to obtain a finished product.
Example 3:
a waterproof printing process based on water-based 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 at 60 ℃ for 2h to obtain coating liquid A; the weight ratio of the stearic acid to the KH-570 modified silicon dioxide to the polydimethylsiloxane to the vinyl polysiloxane is 1:2:3:1, a step of; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating liquid A on the surfaces of two sides of a substrate, vacuum drying at 70 ℃, and curing for 30min at 120 ℃ to obtain a pretreated substrate; the single-sided coating amount of the coating liquid A was 25g/m 2 。
(2) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyl tin dilaurate, heating to 75 ℃, stirring and reacting for 5 hours, adding mixed liquid of N-methylpyrrolidone and dimethylolpropionic acid, continuously preserving heat and reacting for 5 hours, adding trimethylolpropane tri (2-thioglycolate), cooling to 50 ℃, preserving heat for 2 hours to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain the mercapto polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tri (2-thioglycolate) is 1.1:1:1.5, the dibutyl tin dilaurate is used in an amount of 0.5wt% of the polyether polyol, and the dimethylol propionic acid is used in an amount of 28wt% of the polyether polyol. The weight ratio of the N-methylpyrrolidone to the dimethylolpropionic acid is 2:1, a step of; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the amount of the triethylamine is 5 weight percent of the polyurethane prepolymer.
(3) Mixing polyether polyol N210, polydimethylsiloxane and vinyl polysiloxane, adding mixed solution of N-methylpyrrolidone 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, and obtaining the organosilicon modified polyurethane emulsion with the solid content of 35%.
The molar ratio of isophorone diisocyanate to polyether polyol is 1.2; the dosage of the polydimethylsiloxane is 5wt% of the total mass of the system; the vinyl polysiloxane amount is 4wt% of the total mass of the system; the dibutyl tin 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 sulfhydryl polyurethane emulsion and the organosilicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the sulfhydryl 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 a coating liquid B on the surfaces of two sides of the pretreated substrate respectively, and curing by ultraviolet light (400W, 365 nm) for 5-10min to obtain a substrate to be printed; the single-side coating dosage mole ratio of the coating liquid A to the coating liquid B is 5:1.
(5) Taking 70 parts of organosilicon modified polyurethane emulsion, 12 parts of color paste 131-CN (purchased from Kelain chemical Co., ltd.), 12 parts of isopropanol, 3 parts of photoinitiator and 40 parts of deionized water by mass, and uniformly stirring to obtain polyurethane ink;
and (3) taking a substrate to be printed, printing polyurethane ink on the surface, curing for 10min by ultraviolet light (400W, 365 nm), and drying at 60 ℃ to obtain a finished product.
Comparative example 1: with example 2 as a control group, the coating liquid a was not introduced in comparative example 1, and the remaining steps were unchanged.
A waterproof printing process based on water-based polyurethane ink comprises the following steps:
(1) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyl tin dilaurate, heating to 75 ℃, stirring and reacting for 4.5 hours, adding a mixed solution of N-methylpyrrolidone and dimethylolpropionic acid, continuously preserving heat and reacting for 4.5 hours, adding trimethylolpropane tri (2-thioglycolate), cooling to 45 ℃, preserving heat for 2.5 hours to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain the mercapto polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tri (2-thioglycolate) is 1.1:1:1.5, the dibutyl tin dilaurate is used in an amount of 0.5wt% of the polyether polyol, and the dimethylol propionic acid is used in an amount of 28wt% of the polyether polyol. The weight ratio of the N-methylpyrrolidone to the dimethylolpropionic acid is 2:1, a step of; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the amount of the triethylamine is 5 weight percent of the polyurethane prepolymer.
(2) Mixing polyether polyol N210, polydimethylsiloxane and vinyl polysiloxane, adding mixed solution of N-methylpyrrolidone 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 the organosilicon modified polyurethane emulsion with the solid content of 35%.
The molar ratio of isophorone diisocyanate to polyether polyol is 1.2; the dosage of the polydimethylsiloxane is 5wt% of the total mass of the system; the vinyl polysiloxane amount is 4wt% of the total mass of the system; the dibutyl tin 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.
(3) Mixing the sulfhydryl polyurethane emulsion and the organosilicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the sulfhydryl 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 a coating liquid B on the surfaces of two sides of a base material respectively, and curing for 10min by ultraviolet light (400W, 365 nm) to obtain a base material to be printed; the single-sided coating amount of the coating liquid B was 35g/m 2 。
(4) Taking 65 parts by mass of organosilicon modified polyurethane emulsion, 11 parts by mass of color paste 131-CN (purchased from Coryn 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) taking a substrate to be printed, printing polyurethane ink on the surface, curing for 5-10min by ultraviolet light (400W, 365 nm), and drying at 60 ℃ to obtain a finished product.
Comparative example 2: with example 2 as a control, no silicone modification was performed in the polyurethane ink in comparative example 2, and the remaining steps were unchanged.
A waterproof printing process based on water-based 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 at 55 ℃ for 2-3h to obtain coating liquid A; the weight ratio of the stearic acid to the KH-570 modified silicon dioxide to the polydimethylsiloxane to the vinyl polysiloxane is 1:2:3:1, a step of; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating liquid A on the surfaces of two sides of a substrate, vacuum drying at 65 ℃, and curing for 35min at 115 ℃ to obtain a pretreated substrate; the single-sided coating amount of the coating liquid A was 25g/m 2 。
(2) Taking polyether polyol N210 and isophorone diisocyanate, uniformly mixing, adding dibutyl tin dilaurate, heating to 75 ℃, stirring and reacting for 4.5 hours, adding a mixed solution of N-methylpyrrolidone and dimethylolpropionic acid, continuously preserving heat and reacting for 4.5 hours, adding trimethylolpropane tri (2-thioglycolate), cooling to 45 ℃, preserving heat for 2.5 hours to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain the mercapto polyurethane emulsion.
The mass ratio of the polyether polyol to the isophorone diisocyanate to the trimethylolpropane tri (2-thioglycolate) is 1.1:1:1.5, the dibutyl tin dilaurate is used in an amount of 0.5wt% of the polyether polyol, and the dimethylol propionic acid is used in an amount of 28wt% of the polyether polyol. The weight ratio of the N-methylpyrrolidone to the dimethylolpropionic acid is 2:1, a step of; the weight ratio of the polyurethane prepolymer to the deionized water is 1:2, the amount of the triethylamine is 5 weight percent of the polyurethane prepolymer.
(3) And adding polyether polyol N210 into a mixed solution of N-methylpyrrolidone and dimethylolpropionic acid, stirring for 25min at 75 ℃, 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 the polyurethane emulsion with the solid content of 35%.
The molar ratio of isophorone diisocyanate to polyether polyol is 1.2; the dibutyl tin 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 sulfhydryl polyurethane emulsion and the organosilicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B; the mass ratio of the sulfhydryl 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 silicone modified polyurethane emulsion procedure was as in example 2.
Coating a coating liquid B on the surfaces of two sides of the pretreated substrate respectively, and curing for 10min by ultraviolet light (400W, 365 nm) to obtain a substrate to be printed; the single-side coating dosage mole ratio of the coating liquid A to the coating liquid B is 5:1.
(5) Taking 65 parts by mass of polyurethane emulsion, 11 parts by mass of color paste 131-CN (purchased from Coryn 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) taking a substrate to be printed, printing polyurethane ink on the surface, curing for 5-10min by ultraviolet light (400W, 365 nm), and drying at 60 ℃ to obtain a finished product.
Comparative example 3: in comparative example 3, no mercapto group or vinyl group was introduced in the control group of example 2, and the remaining steps were unchanged.
A waterproof printing process based on water-based polyurethane ink comprises the following steps:
(1) Mixing stearic acid, KH-570 modified silicon dioxide and absolute ethyl alcohol, stirring for 25min, adding polydimethylsiloxane, and stirring at 55deg.C for 2-3 hr to obtain coating solution A; the weight ratio of stearic acid to KH-570 modified silicon dioxide to polydimethylsiloxane is 1:2:3, a step of; the dosage of the stearic acid and the absolute ethyl alcohol is 0.1g:30mL.
Coating liquid A on the surfaces of two sides of a substrate, vacuum drying at 65 ℃, and curing for 35min at 115 ℃ to obtain a pretreated substrate; the single-sided coating amount of the coating liquid A was 25g/m 2 。
(2) Mixing polyether polyol N210 and polydimethylsiloxane, adding mixed solution of N-methylpyrrolidone 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 isophorone diisocyanate to polyether polyol is 1.2; the dosage of the polydimethylsiloxane is 5wt% of the total mass of the system; the dibutyl tin 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.
(3) Taking 65 parts by mass of organosilicon modified polyurethane emulsion, 11 parts by mass of color paste 131-CN (purchased from Coryn 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) taking the pretreated substrate, printing polyurethane ink on the surface, and drying at 60 ℃ to obtain a finished product.
Comparative example 4: with comparative example 3 as the control group, the coating liquid a was not applied in comparative example 4, and the remaining steps were unchanged.
A waterproof printing process based on water-based polyurethane ink comprises the following steps:
(1) Mixing polyether polyol N210 and polydimethylsiloxane, adding mixed solution of N-methylpyrrolidone 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 isophorone diisocyanate to polyether polyol is 1.2; the dosage of the polydimethylsiloxane is 5wt% of the total mass of the system; the dibutyl tin 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.
(2) Taking 65 parts by mass of organosilicon modified polyurethane emulsion, 11 parts by mass of color paste 131-CN (purchased from Coryn 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) 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 printed corrugated boards prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to performance test on their surfaces:
1. cutting the printed corrugated board into 5cm multiplied by 10cm samples, putting half of the samples into deionized water, soaking for 24 hours 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. According to GB/T13217.7-2009, the adhesion fastness of polyurethane ink is detected, an adhesive tape method is adopted in the test, the adhesive tape is stuck on the surface of a corrugated board, a roller is rolled back and forth for 3 times, the adhesive tape is placed for 5min, the adhesive tape is uncovered in a rotating way at the speed of 0.8m/s according to the method disclosed in GB/T7707-2008, and the adhesion fastness is observed and calculated.
3. Cutting the printed corrugated board into a sample with the length of 5cm multiplied by 10cm, soaking the sample in deionized water for 24 hours, taking out the sample, wiping the surface moisture of the sample, weighing the mass of the sample before and after soaking, and calculating the water absorption rate of the sample.
| Project | Change after immersion | Attachment fastness | Water absorption rate |
| Example 1 | The ink has no color change and no water staining | 96％ | 5.46％ |
| Example 2 | The ink has no color change and no water staining | 97％ | 4.93％ |
| Example 3 | The ink has no color change and no water staining | 97％ | 5.17％ |
| Comparative example 1 | The ink has no color change and no water staining | 94％ | 11.14％ |
| Comparative example 2 | Slight discoloration of ink and slight staining with water | 89％ | 6.48％ |
| Comparative example 3 | Obvious color change of ink and obvious dyeing with water | 84％ | 7.14％ |
| Comparative example 4 | Slight discoloration of ink and slight staining with water | 90％ | 13.17％ |
Conclusion: the scheme discloses a waterproof printing process based on water-based polyurethane ink, which has reasonable process design and proper component proportion, wherein on one hand, a waterproof layer (coating liquid A) is coated on the surface of a base material (corrugated board or paper box) so as to improve the waterproof and dampproof properties of a product, on the other hand, the setting of a transition layer (coating liquid B) is utilized to ensure the printing effect of the polyurethane ink, and an organosilicon 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 resistance and water resistance, clear ink printing, good ink adhesiveness and higher 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 waterproof printing process based on water-based 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 2-3 hours at 50-60 ℃ to obtain coating liquid A;
coating liquid A on the surfaces of two sides of a substrate, vacuum drying at 60-70 ℃, and curing for 30-40 min at 110-120 ℃ to obtain a pretreated substrate;
(2) Mixing the sulfhydryl polyurethane emulsion and the organosilicon modified polyurethane emulsion, adding a photoinitiator, and uniformly stirring to obtain a coating liquid B;
coating liquid B on the surfaces of two sides of the pretreated base material respectively, and ultraviolet curing for 5-10min to obtain the base material to be printed;
(3) Taking organic silicon modified polyurethane emulsion, color paste, isopropanol, a photoinitiator and deionized water, and uniformly stirring to obtain polyurethane ink;
printing polyurethane ink on the surface of a substrate to be printed, ultraviolet curing for 5-10min, and drying at 60-70 ℃ to obtain a finished product;
in the step (2), the preparation steps of the sulfhydryl polyurethane emulsion are as follows: taking polyether polyol and isophorone diisocyanate, uniformly mixing, adding dibutyl tin dilaurate, heating to 70-75 ℃, stirring and reacting for 4-5 hours, adding mixed solution of N-methylpyrrolidone and dimethylolpropionic acid, continuously carrying out heat preservation and reacting for 4-5 hours, adding trimethylolpropane tri (2-thioglycolate), cooling to 40-50 ℃, carrying out heat preservation for 2-3 hours to obtain a polyurethane prepolymer, adding triethylamine into the polyurethane prepolymer for neutralization, and dispersing with deionized water to obtain a mercapto polyurethane emulsion;
the preparation method of the organosilicon modified polyurethane emulsion comprises the following steps: mixing polyether polyol, polydimethylsiloxane and vinyl polysiloxane, adding N-methyl pyrrolidone and dimethylol propionic acid mixed solution, 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%.
2. The water-proof printing process based on the aqueous polyurethane ink according to claim 1, wherein: in the step (3), the content of each component of the polyurethane ink comprises: 60-70 parts of organosilicon 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 water-proof printing process based on the aqueous polyurethane ink according to 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 2-3 wt% of the total mass of the system.
4. The water-proof printing process based on the aqueous polyurethane ink according to claim 1, wherein: the single-sided coating amount of the coating liquid A is 20-30 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The single-side coating dosage mole ratio of the coating liquid A to the coating liquid B is (5-6): 1.
5. the water-proof printing process based on the aqueous polyurethane ink according to claim 1, wherein: in the step (1), the preparation steps of the vinyl polysiloxane are as follows: mixing phenyl polysiloxane and octamethyl cyclotetrasiloxane, adding a catalyst, adding tetramethyl divinyl disiloxane at 115-120 ℃, reacting for 2-3h, heating to 170-180 ℃, continuing to react for 4-5 h, and vacuum drying after the reaction is finished to obtain vinyl polysiloxane.
6. The water-proof printing process based on the aqueous polyurethane ink according to claim 5, wherein: the catalyst is tetramethyl ammonium hydroxide silicon alkoxide, and the mass ratio of phenyl polysiloxane, octamethyl cyclotetrasiloxane and 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.
7. The water-proof printing process based on the aqueous polyurethane ink according to claim 1, wherein: when the mercapto polyurethane emulsion is prepared, the mass ratio of the polyether polyol, isophorone diisocyanate and trimethylolpropane tri (2-thioglycolate) is 1.1:1:1.5, the dosage of the dibutyl tin dilaurate is 0.4 to 0.5 weight percent of the polyether polyol, and the dosage of the dimethylolpropionic acid is 28 to 30 weight percent of the polyether polyol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210833787.4A CN115139672B (en) | 2022-07-14 | 2022-07-14 | Waterproof printing process based on water-based polyurethane ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210833787.4A CN115139672B (en) | 2022-07-14 | 2022-07-14 | Waterproof printing process based on water-based polyurethane ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115139672A CN115139672A (en) | 2022-10-04 |
| CN115139672B true CN115139672B (en) | 2024-02-13 |
Family
ID=83411972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210833787.4A Active CN115139672B (en) | 2022-07-14 | 2022-07-14 | Waterproof printing process based on water-based polyurethane ink |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115139672B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746622B (en) * | 2022-12-07 | 2023-05-09 | 昆明小松制版印刷有限公司 | High-adhesiveness water-based printing ink and preparation method thereof |
| CN116061283B (en) * | 2023-03-29 | 2023-06-27 | 江苏零界科技集团有限公司 | Waterproof wood composite board and preparation process thereof |
| CN116790153B (en) * | 2023-08-09 | 2023-11-14 | 宝艺新材料股份有限公司 | Moistureproof ink for corrugated board, preparation method and printing method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1223202A (en) * | 1998-01-13 | 1999-07-21 | 大日精化工株式会社 | Ink-jet recording sheet and coating formulation for production of sheet |
| JP2007186645A (en) * | 2006-01-16 | 2007-07-26 | Dainichiseika Color & Chem Mfg Co Ltd | Polyurethane fine particle and method for producing the same |
| CN101049775A (en) * | 2007-05-11 | 2007-10-10 | 天津博苑高新材料有限公司 | High light waterproof ink jet printing sheet material, and application |
| CN101249046A (en) * | 2006-10-25 | 2008-08-27 | 莱雅公司 | Composition for dyeing keratinous fibres comprising a polysiloxane-polyurea block copolymer |
| CN101910329A (en) * | 2007-12-26 | 2010-12-08 | 株式会社理光 | Ink-jet recording ink, ink-jet recording ink set, ink-jet recording ink media set, ink cartridge, ink-jet recording method and ink-jet recording apparatus |
| CN102352151A (en) * | 2011-08-24 | 2012-02-15 | 哈尔滨大东方卷烟材料科技开发有限责任公司 | Water-based ink for plastic printing and preparation method thereof |
| CN102816515A (en) * | 2012-08-14 | 2012-12-12 | 江苏大学 | Aqueous silicon dioxide-fluorinated acrylate polyurethane ultraviolet-curing coating, preparation method and application thereof |
| CN104711902A (en) * | 2015-03-05 | 2015-06-17 | 云南中烟工业有限责任公司 | Water-based ink inner-printing transparent tipping paper and preparation method |
| CN108623779A (en) * | 2017-03-15 | 2018-10-09 | 宇部兴产株式会社 | Polyurethane resin, aqueous polyurethane resin dispersion, its manufacturing method, it is used and its solidfied material |
| CN110669179A (en) * | 2018-07-02 | 2020-01-10 | 中国科学院化学研究所 | Photocuring printing material, method for forming three-dimensional pattern, application and printed matter |
| CN111778776A (en) * | 2020-07-24 | 2020-10-16 | 美盈森集团股份有限公司 | Erasable ink printing paper and preparation method and application thereof |
| CN113910798A (en) * | 2021-09-16 | 2022-01-11 | 美盈森集团股份有限公司 | Paper pulp molding water transfer printing method |
| CN115746622A (en) * | 2022-12-07 | 2023-03-07 | 昆明小松制版印刷有限公司 | High-adhesion water-based printing ink and preparation method thereof |
-
2022
- 2022-07-14 CN CN202210833787.4A patent/CN115139672B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1223202A (en) * | 1998-01-13 | 1999-07-21 | 大日精化工株式会社 | Ink-jet recording sheet and coating formulation for production of sheet |
| JP2007186645A (en) * | 2006-01-16 | 2007-07-26 | Dainichiseika Color & Chem Mfg Co Ltd | Polyurethane fine particle and method for producing the same |
| CN101249046A (en) * | 2006-10-25 | 2008-08-27 | 莱雅公司 | Composition for dyeing keratinous fibres comprising a polysiloxane-polyurea block copolymer |
| CN101049775A (en) * | 2007-05-11 | 2007-10-10 | 天津博苑高新材料有限公司 | High light waterproof ink jet printing sheet material, and application |
| CN101910329A (en) * | 2007-12-26 | 2010-12-08 | 株式会社理光 | Ink-jet recording ink, ink-jet recording ink set, ink-jet recording ink media set, ink cartridge, ink-jet recording method and ink-jet recording apparatus |
| CN102352151A (en) * | 2011-08-24 | 2012-02-15 | 哈尔滨大东方卷烟材料科技开发有限责任公司 | Water-based ink for plastic printing and preparation method thereof |
| CN102816515A (en) * | 2012-08-14 | 2012-12-12 | 江苏大学 | Aqueous silicon dioxide-fluorinated acrylate polyurethane ultraviolet-curing coating, preparation method and application thereof |
| CN104711902A (en) * | 2015-03-05 | 2015-06-17 | 云南中烟工业有限责任公司 | Water-based ink inner-printing transparent tipping paper and preparation method |
| CN108623779A (en) * | 2017-03-15 | 2018-10-09 | 宇部兴产株式会社 | Polyurethane resin, aqueous polyurethane resin dispersion, its manufacturing method, it is used and its solidfied material |
| CN110669179A (en) * | 2018-07-02 | 2020-01-10 | 中国科学院化学研究所 | Photocuring printing material, method for forming three-dimensional pattern, application and printed matter |
| CN111778776A (en) * | 2020-07-24 | 2020-10-16 | 美盈森集团股份有限公司 | Erasable ink printing paper and preparation method and application thereof |
| CN113910798A (en) * | 2021-09-16 | 2022-01-11 | 美盈森集团股份有限公司 | Paper pulp molding water transfer printing method |
| CN115746622A (en) * | 2022-12-07 | 2023-03-07 | 昆明小松制版印刷有限公司 | High-adhesion water-based printing ink and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115139672A (en) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115139672B (en) | Waterproof printing process based on water-based polyurethane ink | |
| CN108410347B (en) | Water-based UV (ultraviolet) coating for LED (light-emitting diode) light source | |
| CN103709364B (en) | The preparation method of a kind of Quaternary Ammonium Salt of Chitosan and the composite modified cation water-borne polyurethane color fixing agent of organosilicon | |
| EP2417296B9 (en) | A method for treating a surface of a substrate | |
| CN102604042B (en) | Aqueous cationic polyurethane resin for transfer aluminum plating and preparation method thereof | |
| CN101824135A (en) | Preparation method and application of terminated-type cation water-borne polyurethane color fixing agent | |
| CN104231209A (en) | Preparation method for high-hardness waterborne polyurethane dispersion | |
| CN107129565B (en) | Preparation process of waterborne polyurethane emulsion | |
| CN114539888B (en) | Strippable dual-curing coating and preparation method thereof | |
| CN109371687B (en) | High-flexibility waterborne polyurethane finishing agent for textiles and preparation method thereof | |
| CN111607320A (en) | Waterborne polyurethane-silica sol composite antifogging agent and preparation method and application thereof | |
| CN115820066B (en) | Water-based coating for thermal transfer ink-jet printing, and preparation method and application thereof | |
| DE112010001964T5 (en) | A photocatalyst supporting sheet and primer for the photocatalyst assisting sheet | |
| JPH11172197A (en) | Paper-releasing composition having printing suitability | |
| CN112829489B (en) | Printing process for UV flash three-dimensional pyrograph packaging box | |
| CN116875169B (en) | Waterproof corrosion-resistant water paint and preparation method thereof | |
| CN111647306B (en) | In situ generation of organized SiO 2 Environment-friendly enhanced waterborne polyurethane ink and preparation method thereof | |
| JPH06136321A (en) | Production of polyurethane/silica hybrid and alcoholic sol solution | |
| CN115746622B (en) | High-adhesiveness water-based printing ink and preparation method thereof | |
| CN108530603B (en) | Mica modified waterborne polyurethane emulsion, adhesive and preparation method thereof | |
| CN107446107A (en) | A kind of aqueous polyurethane without organotin and preparation method thereof | |
| CN114855503A (en) | Biodegradable water-based plastic replacement oil and preparation method thereof | |
| CN115386289B (en) | Water-based printable cold-stamping color layer coating and preparation method thereof | |
| CN113667310B (en) | Liquid silicone rubber and preparation method and application thereof | |
| CN108034399A (en) | A kind of preparation method of the cross-linking modified polycarbonate waterborne polyurethane adhesive of uvioresistant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |