CN114907719A - Waterborne polyurethane printing ink and printing method thereof - Google Patents
Waterborne polyurethane printing ink and printing method thereof Download PDFInfo
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- CN114907719A CN114907719A CN202210721172.2A CN202210721172A CN114907719A CN 114907719 A CN114907719 A CN 114907719A CN 202210721172 A CN202210721172 A CN 202210721172A CN 114907719 A CN114907719 A CN 114907719A
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- 238000007639 printing Methods 0.000 title claims abstract description 96
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 57
- 239000004814 polyurethane Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000839 emulsion Substances 0.000 claims abstract description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 20
- -1 methyl alcohol amine Chemical class 0.000 claims abstract description 19
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 239000002562 thickening agent Substances 0.000 claims abstract description 19
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 18
- 239000000113 methacrylic resin Substances 0.000 claims abstract description 18
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 18
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 17
- 239000000080 wetting agent Substances 0.000 claims abstract description 17
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims abstract description 16
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 16
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 5
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 5
- 229960004853 betadex Drugs 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 25
- 239000011087 paperboard Substances 0.000 claims description 20
- 239000001993 wax Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 12
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical class OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000009775 high-speed stirring Methods 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000004200 microcrystalline wax Substances 0.000 claims description 4
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 4
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 4
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004203 carnauba wax Substances 0.000 claims description 2
- 235000013869 carnauba wax Nutrition 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 244000269722 Thea sinensis Species 0.000 claims 2
- 241001122767 Theaceae Species 0.000 abstract description 14
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 238000007781 pre-processing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 50
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- 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
-
- 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/108—Hydrocarbon resins
-
- 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
- C09D11/12—Printing inks based on waxes or bitumen
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention belongs to the technical field of ink printing, and provides waterborne polyurethane printing ink and a printing method thereof, wherein the waterborne polyurethane printing ink comprises the following components in parts by weight: 15-25 parts of modified polybutadiene resin, 20-30 parts of polyurethane resin, 15-25 parts of water-soluble methacrylic resin, 80-120 parts of deionized water, 10-15 parts of inorganic pigment, 3-8 parts of water-based wax emulsion, 2-6 parts of methyl alcohol amine neutralizer, 2-3 parts of methylated-beta-cyclodextrin, 3-5 parts of triethanolamine, 1-2 parts of tea polyphenol, 0.5-1 part of alcohol ether sulfosuccinic acid monoester disodium salt, 0.1-0.3 part of nano tin dioxide, 0.2-0.5 part of thickening agent, 0.2-0.5 part of defoaming agent and 0.2-0.5 part of wetting agent. According to the invention, through the mutual synergistic effect of the components, the preprocessing treatment of the raw materials and the control of the temperature, the components interact according to a certain proportion, so that the average particle size of polyurethane emulsion particles in the printing ink is smaller, the storage stability is effectively improved, and the stability, the gloss and the adhesive force of the printing ink are improved.
Description
Technical Field
The invention relates to the technical field of ink printing, in particular to waterborne polyurethane printing ink and a preparation method and a printing method thereof.
Background
The printing ink is a common coloring material for printed products, is an important material applied to the printing industry, generally comprises components such as pigment, bonding material, filler and the like, is a colored paste-like adhesive body with certain fluidity, and is mainly used for various printings such as books and periodicals, packaging decoration, building decoration and the like. The ink adopted in the domestic traditional technology is basically solvent-based ink, and the solvent-based ink easily volatilizes a large amount of benzene and ketone gases polluting air in the printing process, thereby causing great harm to the health of workers, and also has the defects of uneven viscosity control, poor adhesion with a base material, high price of part of ink with better performance and the like.
At present, in order to overcome the problems of uneven viscosity control, poor adhesion with a base material and the like of the traditional solvent-based ink, a plurality of waterborne polyurethane inks have been developed on the market, and the waterborne polyurethane is a binary colloidal resin formed by introducing hydrophilic groups on polyurethane molecular chains to endow the polyurethane molecular chains with hydrophilicity and then dispersing the polyurethane molecular chains in water. The water-based ink is mainly applied to packaging printing at present, and the printing mode is mainly gravure printing. Compared with solvent-based ink, the water-based ink has extremely low VOC content, greatly improves the working environment of ink manufacturers and printing operators, and reduces the harm of harmful substances to the bodies of the ink manufacturers and the printing operators.
However, the existing water-based polyurethane ink has high viscosity and low solid content due to the introduction of hydrophilic groups; meanwhile, the average particle size of emulsion particles of the waterborne polyurethane is large, and the storage stability after long-time storage is poor. Therefore, there is a need for improvement of the existing aqueous polyurethane ink to improve the storage stability of the existing polyurethane ink while improving the water resistance and gloss of the existing polyurethane ink.
Disclosure of Invention
The invention provides waterborne polyurethane printing ink with smaller average particle size of emulsion particles and better storage stability and a printing method thereof, aiming at solving the defects of the existing waterborne polyurethane printing ink.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a waterborne polyurethane printing ink, which comprises the following components in parts by weight: 15-25 parts of modified polybutadiene resin, 20-30 parts of polyurethane resin, 15-25 parts of water-soluble methacrylic resin, 80-120 parts of deionized water, 10-15 parts of inorganic pigment, 3-8 parts of water-based wax emulsion, 2-6 parts of methyl alcohol amine neutralizer, 2-3 parts of methylated-beta-cyclodextrin, 3-5 parts of triethanolamine, 1-2 parts of tea polyphenol, 0.5-1 part of alcohol ether sulfosuccinic acid monoester disodium salt, 0.1-0.3 part of nano tin dioxide, 0.2-0.5 part of thickening agent, 0.2-0.5 part of defoaming agent and 0.2-0.5 part of wetting agent.
Preferably, the aqueous polyurethane printing ink comprises the following components in parts by weight: 18-24 parts of modified polybutadiene resin, 22-28 parts of polyurethane resin, 17-23 parts of water-soluble methacrylic resin, 85-110 parts of deionized water, 11-14 parts of inorganic pigment, 4-6 parts of water-based wax emulsion, 3-5 parts of methyl alcohol amine neutralizer, 2.2-2.8 parts of methylated-beta-cyclodextrin, 3.5-4.5 parts of triethanolamine, 1.2-1.8 parts of tea polyphenol, 0.6-0.8 part of alcohol ether sulfosuccinic acid monoester disodium salt, 0.15-0.25 part of nano tin dioxide, 0.25-0.45 part of thickening agent, 0.25-0.45 part of defoaming agent and 0.25-0.45 part of wetting agent.
More preferably, the aqueous polyurethane printing ink comprises the following components in parts by weight: 20-22 parts of modified polybutadiene resin, 24-26 parts of polyurethane resin, 18-22 parts of water-soluble methacrylic resin, 95-110 parts of deionized water, 12-14 parts of inorganic pigment, 4.5-5.5 parts of water-based wax emulsion, 3.6-4.5 parts of methyl alcohol amine neutralizer, 2.3-2.6 parts of methylated-beta-cyclodextrin, 3.8-4.2 parts of triethanolamine, 1.5-1.7 parts of tea polyphenol, 0.6-0.7 part of sulfosuccinic acid monoester disodium salt, 0.18-0.22 part of nano tin dioxide, 0.32-0.40 part of thickening agent, 0.25-0.30 part of defoaming agent and 0.38-0.42 part of wetting agent.
Preferably, the molecular weight of the modified polybutadiene resin is 40000-50000, the molecular weight of the polyurethane resin is 20000-30000, and the molecular weight of the water-soluble methacrylic resin is 50000-60000.
Preferably, the inorganic pigment is prepared from titanium dioxide and grey tile powder which are subjected to dry emulsification modification by a silane coupling agent according to the mass ratio of 1: 0.5 to 0.8, and an average particle size of 50 to 100 μm.
Preferably, the inorganic pigment is prepared by mixing titanium dioxide and green tile powder which are emulsified and modified by a silane coupling agent in a dry method according to a mass ratio of 1: 0.6-0.7, and the average particle size is 60-90 μm.
More preferably, the inorganic pigment is prepared by mixing titanium dioxide and green tile powder which are emulsified and modified by a silane coupling agent in a dry method according to a mass ratio of 1: 0.65, and the average particle size is 70-80 μm.
Preferably, the silane coupling agent is KH560 or KH550, and the mass ratio of the silane coupling agent to the titanium dioxide or the grey tile powder is 1: 0.1-0.2.
More preferably, the silane coupling agent is KH560, and the mass ratio of the KH560 to the titanium dioxide or the grey tile powder is 1: 0.16.
Preferably, the aqueous wax emulsion is one of a microcrystalline wax emulsion, a carnauba wax emulsion, a polyethylene wax emulsion, and an oxidized polyethylene wax emulsion.
More preferably, the aqueous wax emulsion is a combination of a microcrystalline wax emulsion and an oxidized polyethylene wax emulsion, and the mass ratio of the microcrystalline wax emulsion to the oxidized polyethylene wax emulsion is 1: 2-3.
Preferably, the nano tin dioxide is superfine nano tin dioxide with the particle size of 50-100 nm.
Preferably, the thickener consists of hydroxyethyl cellulose and a polyurethane associative thickener according to the mass ratio of 1: 3-5.
Preferably, the defoaming agent consists of pentaerythritol stearate and polyoxypropylene ethylene oxide glycerol ether in a mass ratio of 1: 0.4-0.8.
Preferably, the wetting agent consists of polyethylene glycol ether and sodium dodecyl benzene sulfonate in a mass ratio of 1: 1-1.5.
The second aspect of the invention provides a preparation method of the waterborne polyurethane printing ink, which comprises the following steps:
(1) sequentially adding modified polybutadiene resin, polyurethane resin and water-soluble methacrylic resin in a formula ratio into at least 2/3 deionized water, heating to 50-65 ℃, and stirring at 200-300 r/min for 5-10 min to obtain a mixture A with the solid content of 40-60%;
(2) placing the inorganic pigment consisting of the modified titanium dioxide and the grey tile powder, the alcohol ether sulfosuccinic acid monoester disodium salt and the nano tin dioxide into a sand mill according to the formula ratio, and sanding for 10-15 min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding the water-based wax emulsion, the methyl alcohol amine neutralizer, the methylated beta-cyclodextrin, the triethanolamine, the tea polyphenol and the rest deionized water into a high-speed stirrer according to the formula ratio, stirring for 5-10 min at 35-40 ℃ at 400-500 r/min, adding the mixture A, and continuing stirring for 20-30 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 5-20 min at the temperature of 50-60 ℃ and at the speed of 1000-1200 r/min;
(5) and (4) continuously adding the thickening agent, the defoaming agent and the wetting agent in the formula ratio into the high-speed stirrer in the step (4), and continuously stirring for 2-3 min at the speed of 500-600 r/min after the temperature of the materials reaches the normal temperature to obtain the high-speed stirring material.
The third aspect of the invention provides a printing method of waterborne polyurethane printing ink, which is used for printing the surface of a paperboard on a paperboard printing machine, wherein the temperature of a printing roller is 70-75 ℃, the drying temperature is 50-60 ℃, and the treatment time is 0.5-1 h.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
(1) the modified polybutadiene resin, the polyurethane resin and the water-soluble methacrylic resin are adopted to prepare a mixture A in advance as a polyurethane resin emulsion, and an inorganic pigment, an alcohol ether sulfosuccinic acid monoester disodium salt and a mixture B of nano tin dioxide are matched, so that the average particle size of emulsion particles in the prepared printing ink is smaller, and the storage stability is effectively improved;
(2) by adding the water-based wax emulsion, the methyl ethanolamine neutralizer, the methylated beta-cyclodextrin, the triethanolamine and the tea polyphenol into the polyurethane emulsion and interacting with the components in the mixture A and the mixture B, the printing ink has a certain antibacterial and mildewproof effect while the water resistance and the glossiness of the printing ink are improved, and the color durability is improved;
(3) the waterborne polyurethane printing ink disclosed by the invention adopts a specific preparation process, the compatibility of each component is good through the preprocessing treatment on the raw materials and the control on the temperature, and the various components interact according to a certain proportion, so that the stability, the gloss and the adhesive force of the printing ink are improved.
Detailed Description
The present invention will now be described in detail and specifically by the following examples to provide a better understanding of the present invention, but the following examples are not intended to limit the scope of the present invention.
Example 1
The preparation method of the waterborne polyurethane printing ink comprises the following steps:
(1) sequentially adding 15 parts of modified polybutadiene resin, 30 parts of polyurethane resin and 20 parts of water-soluble methacrylic resin into 70 parts of deionized water, heating to 55 ℃, and stirring at 250r/min for 8min to obtain a mixture A;
(2) placing the inorganic pigment consisting of 6 parts of modified titanium dioxide and 4 parts of grey tile powder, 0.5 part of alcohol ether sulfosuccinic acid monoester disodium salt and 0.1 part of nano tin dioxide in a sand mill, and sanding for 15min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding 5 parts of water-based wax emulsion, 3 parts of methyl alcohol amine neutralizer, 3 parts of methylated beta-cyclodextrin, 3 parts of triethanolamine, 2 parts of tea polyphenol and 30 parts of deionized water into a high-speed stirrer, stirring at 35 ℃ and 420r/min for 10min, adding the mixture A, and continuing to stir for 20 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 10min at the temperature of 50 ℃ and the speed of 1200 r/min;
(5) and (4) continuously adding 0.3 part of thickening agent, 0.2 part of defoaming agent and 0.3 part of wetting agent into the high-speed stirrer in the step (4), and continuously stirring for 3min at 600r/min after the temperature of the materials reaches normal temperature to obtain the high-speed stirring material.
(6) And (3) printing the surface of the paperboard on a paperboard printing machine by adopting the waterborne polyurethane printing ink prepared in the step (5), wherein the temperature of a printing roller is 70 ℃, the drying treatment temperature is 50 ℃, and the treatment time is 0.5 h.
Example 2
The preparation method of the waterborne polyurethane printing ink comprises the following steps:
(1) sequentially adding 15 parts of modified polybutadiene resin, 30 parts of polyurethane resin and 20 parts of water-soluble methacrylic resin into 70 parts of deionized water, heating to 55 ℃, and stirring at 250r/min for 8min to obtain a mixture A;
(2) placing inorganic pigment consisting of 6 parts of titanium dioxide and 4 parts of green tile powder, 0.5 part of alcohol ether sulfosuccinic acid monoester disodium salt and 0.1 part of nano tin dioxide in a sand mill, and sanding for 15min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding 5 parts of water-based wax emulsion, 3 parts of methyl alcohol amine neutralizer, 3 parts of methylated beta-cyclodextrin, 3 parts of triethanolamine, 2 parts of tea polyphenol and 30 parts of deionized water into a high-speed stirrer, stirring for 10min at 35 ℃ at 420r/min, adding the mixture A, and continuing stirring for 20 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 10min at the temperature of 50 ℃ and the speed of 1200 r/min;
(5) and (4) continuously adding 0.3 part of thickening agent, 0.2 part of defoaming agent and 0.3 part of wetting agent into the high-speed stirrer in the step (4), and continuously stirring for 3min at 600r/min after the temperature of the materials reaches normal temperature to obtain the high-speed stirring material.
(6) And (3) printing the surface of the paperboard on a paperboard printing machine by adopting the waterborne polyurethane printing ink prepared in the step (5), wherein the temperature of a printing roller is 70 ℃, the drying treatment temperature is 50 ℃, and the treatment time is 0.5 h.
Example 3
The preparation method of the waterborne polyurethane printing ink comprises the following steps:
(1) sequentially adding 18 parts of modified polybutadiene resin, 25 parts of polyurethane resin and 18 parts of water-soluble methacrylic resin into 85 parts of deionized water, heating to 65 ℃, and stirring at 200-300 r/min for 8min to obtain a mixture A;
(2) placing an inorganic pigment consisting of 7 parts of modified titanium dioxide and 5 parts of green tile powder, 1 part of alcohol ether sulfosuccinic acid monoester disodium salt and 0.3 part of nano tin dioxide in a sand mill, and sanding for 10min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding 4 parts of water-based wax emulsion, 4 parts of methyl alcohol amine neutralizer, 2.5 parts of methylated beta-cyclodextrin, 3.5 parts of triethanolamine, 1.5 parts of tea polyphenol and 20 parts of deionized water into a high-speed stirrer, stirring at 38 ℃ and 450r/min for 5min, adding the mixture A, and continuing stirring for 30 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 10min at the temperature of 55 ℃ and at the speed of 1100 r/min;
(5) and (4) continuously adding 0.3 part of thickening agent, 0.4 part of defoaming agent and 0.3 part of wetting agent into the high-speed stirrer in the step (4), and continuously stirring for 3min at 600r/min after the temperature of the materials reaches normal temperature to obtain the high-speed stirring material.
(6) And (3) printing the surface of the paperboard on a paperboard printing machine by adopting the waterborne polyurethane printing ink prepared in the step (5), wherein the temperature of a printing roller is 70 ℃, the drying treatment temperature is 60 ℃, and the treatment time is 0.5 h.
Example 4
The preparation method of the waterborne polyurethane printing ink comprises the following steps:
(1) sequentially adding 18 parts of modified polybutadiene resin, 25 parts of polyurethane resin and 18 parts of water-soluble methacrylic resin into 85 parts of deionized water, heating to 65 ℃, and stirring at 200-300 r/min for 8min to obtain a mixture A;
(2) placing an inorganic pigment consisting of 7 parts of titanium dioxide and 5 parts of green tile powder, 1 part of alcohol ether sulfosuccinic acid monoester disodium salt and 0.3 part of nano tin dioxide in a sand mill, and sanding for 10min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding 4 parts of water-based wax emulsion, 4 parts of methyl alcohol amine neutralizer, 2.5 parts of methylated beta-cyclodextrin, 3.5 parts of triethanolamine, 1.5 parts of tea polyphenol and 20 parts of deionized water into a high-speed stirrer, stirring at 38 ℃ and 450r/min for 5min, adding the mixture A, and continuing stirring for 30 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 10min at the temperature of 55 ℃ and at the speed of 1100 r/min;
(5) and (4) continuously adding 0.3 part of thickening agent, 0.4 part of defoaming agent and 0.3 part of wetting agent into the high-speed stirrer in the step (4), and continuously stirring for 3min at 600r/min after the temperature of the materials reaches normal temperature to obtain the high-speed stirring material.
(6) And (3) printing the surface of the paperboard on a paperboard printing machine by adopting the waterborne polyurethane printing ink prepared in the step (5), wherein the temperature of a printing roller is 70 ℃, the drying treatment temperature is 60 ℃, and the treatment time is 0.5 h.
Example 5
The preparation method of the waterborne polyurethane printing ink comprises the following steps:
(1) sequentially adding 20 parts of modified polybutadiene resin, 22 parts of polyurethane resin and 125 parts of water-soluble methacrylic resin into 75 parts of deionized water, heating to 65 ℃, and stirring at 300r/min for 10min to obtain a mixture A;
(2) placing the inorganic pigment consisting of 10 parts of modified titanium dioxide and 5 parts of grey tile powder, 1 part of alcohol ether sulfosuccinic acid monoester disodium salt and 0.2 part of nano tin dioxide in a sand mill, and sanding for 15min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding 6 parts of water-based wax emulsion, 5 parts of methyl alcohol amine neutralizer, 2.5 parts of methylated beta-cyclodextrin, 3.8 parts of triethanolamine, 1.6 parts of tea polyphenol and 25 parts of deionized water into a high-speed stirrer, stirring at 40 ℃ for 5min at 500r/min, adding the mixture A, and continuing to stir for 20 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 10min at 55 ℃ at 1200 r/min;
(5) and (4) continuously adding 0.3 part of thickening agent, 0.2 part of defoaming agent and 0.4 part of wetting agent into the high-speed stirrer in the step (4), and continuously stirring for 3min at 550r/min after the temperature of the materials reaches normal temperature to obtain the high-speed stirring material.
(6) And (3) printing the surface of the paperboard on a paperboard printing machine by adopting the waterborne polyurethane printing ink prepared in the step (5), wherein the temperature of a printing roller is 70 ℃, the drying treatment temperature is 55 ℃, and the treatment time is 0.5-1 h.
Example 6
The preparation method of the waterborne polyurethane printing ink comprises the following steps:
(1) sequentially adding 22 parts of modified polybutadiene resin, 25 parts of polyurethane resin and 18 parts of water-soluble methacrylic resin into 80 parts of deionized water, heating to 55 ℃, and stirring at 200-300 r/min for 8min to obtain a mixture A;
(2) placing the inorganic pigment consisting of 10 parts of modified titanium dioxide and 5 parts of grey tile powder, 0.8 part of alcohol ether sulfosuccinic acid monoester disodium salt and 0.2 part of nano tin dioxide in a sand mill, and sanding for 12min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding 6 parts of water-based wax emulsion, 4 parts of methyl alcohol amine neutralizer, 2.6 parts of methylated beta-cyclodextrin, 4 parts of triethanolamine, 2 parts of tea polyphenol and 40 parts of deionized water into a high-speed stirrer, stirring at 40 ℃ and 500r/min for 5min, adding the mixture A, and continuing stirring for 22 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 20min at the temperature of 60 ℃ and at the speed of 1000 r/min;
(5) and (4) continuously adding 0.4 part of thickening agent, 0.3 part of defoaming agent and 0.4 part of wetting agent into the high-speed stirrer in the step (4), and continuously stirring for 3min at 600r/min after the temperature of the materials reaches normal temperature to obtain the high-speed stirring material.
(6) And (4) printing the surface of the paperboard on a paperboard printing machine by adopting the waterborne polyurethane printing ink prepared in the step (5), wherein the temperature of a printing roller is 72 ℃, the drying treatment temperature is 58 ℃, and the treatment time is 0.5 h.
Example 7
The preparation method of the waterborne polyurethane printing ink comprises the following steps:
(1) sequentially adding 25 parts of modified polybutadiene resin, 22 parts of polyurethane resin and 15 parts of water-soluble methacrylic resin into 80 parts of deionized water, heating to 65 ℃, and stirring at 280r/min for 8min to obtain a mixture A;
(2) placing 15 parts of inorganic pigment consisting of 10 parts of modified titanium dioxide and cyan tile powder, 1 part of alcohol ether sulfosuccinic acid monoester disodium salt and 0.3 part of nano tin dioxide in a sand mill, and sanding for 15min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding 8 parts of aqueous wax emulsion, 6 parts of methyl alcohol amine neutralizer, 3 parts of methylated beta-cyclodextrin, 5 parts of triethanolamine, 2 parts of tea polyphenol and 40 parts of deionized water into a high-speed stirrer, stirring at 35 ℃ and 450r/min for 10min, adding the mixture A, and continuing to stir for 20 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 20min at the temperature of 55 ℃ at the speed of 1100 r/min;
(5) and (4) continuously adding 0.4 part of thickening agent, 0.5 part of defoaming agent and 0.5 part of wetting agent into the high-speed stirrer in the step (4), and continuously stirring for 3min at 600r/min after the temperature of the materials reaches normal temperature to obtain the high-speed stirring material.
(6) And (3) printing the surface of the paperboard on a paperboard printing machine by adopting the waterborne polyurethane printing ink prepared in the step (5), wherein the temperature of a printing roller is 70 ℃, the drying treatment temperature is 50 ℃, and the treatment time is 1 h.
Example 8
The preparation method of the waterborne polyurethane printing ink comprises the following steps:
(1) sequentially adding 25 parts of modified polybutadiene resin, 30 parts of polyurethane resin and 20 parts of water-soluble methacrylic resin into 80 parts of deionized water, heating to 65 ℃, and stirring at 200-300 r/min for 10min to obtain a mixture A;
(2) placing an inorganic pigment consisting of 8.5 parts of modified titanium dioxide and 6.5 parts of grey tile powder, 1 part of alcohol ether sulfosuccinic acid monoester disodium salt and 0.25 part of nano tin dioxide in a sand mill, and sanding for 15min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding 6 parts of water-based wax emulsion, 6 parts of methyl alcohol amine neutralizer, 2.8 parts of methylated beta-cyclodextrin, 4.2 parts of triethanolamine, 1.8 parts of tea polyphenol and 40 parts of deionized water into a high-speed stirrer, stirring at 40 ℃ at 500r/min for 10min, adding the mixture A, and continuing to stir for 230 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 15min at the temperature of 60 ℃ and the speed of 1200 r/min;
(5) and (4) continuously adding 0.5 part of thickening agent, 0.4 part of defoaming agent and 0.4 part of wetting agent into the high-speed stirrer in the step (4), and continuously stirring for 2min at 500r/min after the temperature of the materials reaches normal temperature to obtain the high-speed stirring material.
(6) And (3) printing the surface of the paperboard on a paperboard printing machine by adopting the waterborne polyurethane printing ink prepared in the step (5), wherein the temperature of a printing roller is 70 ℃, the drying treatment temperature is 60 ℃, and the treatment time is 1 h.
Performance testing
The aqueous polyurethane printing inks prepared in examples 1 to 8 were subjected to particle size test, glossiness, surface tension, tinting strength, adhesion, storage stability, and the like, respectively, following the relevant standards.
Specifically, a dynamic light scattering instrument is adopted for particle size test, a plurality of samples are stored at room temperature for storage stability, one sample is taken out every fixed time, the samples are centrifuged for 15min at 6000rpm, whether demulsification is layered or not is observed, and the number of days (d) before demulsification is layered is recorded as an index for evaluating storage stability. Specific test data are shown in table 1 below.
Table 1 results of performance test of each example
As can be seen from the table 1, the average particle size of the polyurethane emulsion particles in the aqueous polyurethane printing ink prepared by the method is smaller, and the storage stability is effectively improved; meanwhile, through the mutual synergistic effect of the components, the stability, the gloss and the adhesive force of the printing ink are greatly improved.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. The waterborne polyurethane printing ink is characterized by comprising the following components in parts by weight: 15-25 parts of modified polybutadiene resin, 20-30 parts of polyurethane resin, 15-25 parts of water-soluble methacrylic resin, 80-120 parts of deionized water, 10-15 parts of inorganic pigment, 3-8 parts of water-based wax emulsion, 2-6 parts of methyl alcohol amine neutralizer, 2-3 parts of methylated-beta-cyclodextrin, 3-5 parts of triethanolamine, 1-2 parts of tea polyphenol, 0.5-1 part of alcohol ether sulfosuccinic acid monoester disodium salt, 0.1-0.3 part of nano tin dioxide, 0.2-0.5 part of thickening agent, 0.2-0.5 part of defoaming agent and 0.2-0.5 part of wetting agent.
2. The aqueous polyurethane printing ink according to claim 1, wherein the modified polybutadiene resin has a molecular weight of 40000 to 50000, the polyurethane resin has a molecular weight of 20000 to 30000, and the water-soluble methacrylic resin has a molecular weight of 50000 to 60000.
3. The aqueous polyurethane printing ink as claimed in claim 1, wherein the inorganic pigment is prepared by mixing titanium dioxide powder and green tile powder which are emulsified and modified by a silane coupling agent in a dry method according to a mass ratio of 1: 0.5 to 0.8, and an average particle size of 50 to 100 μm.
4. The aqueous polyurethane printing ink of claim 1, wherein the aqueous wax emulsion is one of a microcrystalline wax emulsion, a carnauba wax emulsion, a polyethylene wax emulsion, and an oxidized polyethylene wax emulsion.
5. The waterborne polyurethane printing ink as claimed in claim 1, wherein the nano tin dioxide is ultra-fine nano tin dioxide, and the particle size of the nano tin dioxide is 50-100 nm.
6. The aqueous polyurethane printing ink according to claim 1, wherein the thickener is composed of hydroxyethyl cellulose and a polyurethane associative thickener in a mass ratio of 1:3 to 5.
7. The aqueous polyurethane printing ink according to claim 1, wherein the antifoaming agent is composed of pentaerythritol stearate and polyoxypropylene ethylene oxide glycerol ether in a mass ratio of 1: 0.4-0.8.
8. The aqueous polyurethane printing ink as claimed in claim 1, wherein the wetting agent is composed of polyethylene glycol ether and sodium dodecylbenzenesulfonate in a mass ratio of 1:1 to 1.5.
9. A process for the preparation of an aqueous polyurethane printing ink according to any one of claims 1 to 8, characterized in that it comprises the following steps:
(1) sequentially adding the modified polybutadiene resin, the polyurethane resin and the water-soluble methacrylic resin in the formula ratio into at least 2/3 deionized water, heating to 50-65 ℃, and stirring at 200-300 r/min for 5-10 min to obtain a mixture A with the solid content of 40-60%;
(2) placing the inorganic pigment consisting of the modified titanium dioxide and the grey tile powder, the alcohol ether sulfosuccinic acid monoester disodium salt and the nano tin dioxide into a sand mill according to the formula ratio, and sanding for 10-15 min to obtain a mixture B with the average particle size of 0.5-5 mu m;
(3) adding the water-based wax emulsion, the methyl alcohol amine neutralizer, the methylated beta-cyclodextrin, the triethanolamine, the tea polyphenol and the rest deionized water into a high-speed stirrer according to the formula ratio, stirring for 5-10 min at 35-40 ℃ at 400-500 r/min, adding the mixture A, and continuing stirring for 20-30 min;
(4) after stirring, adding the mixture B into the high-speed stirrer in the step (3), and continuously stirring for 5-20 min at the temperature of 50-60 ℃ and at the speed of 1000-1200 r/min;
(5) and (4) continuously adding the thickening agent, the defoaming agent and the wetting agent in the formula ratio into the high-speed stirrer in the step (4), and continuously stirring for 2-3 min at the speed of 500-600 r/min after the temperature of the materials reaches the normal temperature to obtain the high-speed stirring material.
10. A printing method of the waterborne polyurethane printing ink is characterized in that the waterborne polyurethane printing ink as described in any one of claims 1 to 8 is used for printing the surface of a paperboard on a paperboard printing machine, the temperature of a printing roller is 70-75 ℃, the drying treatment temperature is 50-60 ℃, and the treatment time is 0.5-1 h.
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