CN111471157B - Water-based polyurethane ink binder and preparation method and application thereof - Google Patents
Water-based polyurethane ink binder and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
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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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
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- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/005—Carbon black
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- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
- C09D17/008—Titanium dioxide
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Abstract
The invention discloses a water-based polyurethane ink binder and a preparation method and application thereof, wherein the method comprises the following steps: preparing NCO-terminated polyurethane prepolymers A, B and C; mixing the NCO-terminated polyurethane prepolymer A and B obtained in the step, cooling to 30-40 ℃ to obtain a polyurethane prepolymer, and adding water to disperse the polyurethane prepolymer to obtain a mixed solution; and (3) adding the mixed solution obtained in the step (S2) into an aqueous solution containing an amine chain extender under a stirring state for chain extension, then dripping the NCO-terminated polyurethane prepolymer C into the aqueous solution, adding a silane coupling agent for crosslinking reaction, removing the solvent, and then adjusting the solid content with water to obtain the aqueous polyurethane ink binder. The modified waterborne polyurethane synthetic structure disclosed by the invention is designed, so that the release effect of the polyurethane resin on the solvent and water is improved, the performance requirement for reducing the solvent residue can be met, the requirement for residual solvent of food and medicine packaging products can be completely met, and the performance index requirement of food and medicine can be met.
Description
Technical Field
The invention relates to the technical field of printing, in particular to an ink vehicle and a preparation method and application thereof.
Background
Printing (Printing) is a technique of transferring ink to the surface of a material such as paper, fabric, plastic, or leather by performing processes such as plate making, inking, and pressing on an original such as characters, pictures, photographs, and forgery prevention, and thereby copying the content of the original in bulk. Because a large amount of organic solvent type ink is required to be used in the printing process, and the organic solvent type ink contains 50-60% of volatile components, gas generated by volatilization of the organic solvent enters the body of a worker through breathing, the liver and the nervous system of a human body are damaged, and the environment is greatly damaged. With the continuous development and progress of economy, science and technology and culture of the society, the green environmental protection concept is more and more emphasized by the society, and related laws and regulations are also introduced by the nation to promote the green environmental protection transformation of the printing industry. In recent years, aqueous ink is developed rapidly, but mainly surface printing ink and common composite ink are used as main ink, an ink system mainly uses aqueous acrylic acid, aqueous film polyurethane ink is relatively less, and particularly, the amount of the aqueous film composite ink capable of being steamed at high temperature is little.
The existing water-based acrylic acid system ink has good gloss, good film-forming property and low content of Volatile Organic Compounds (VOC); however, due to the limitation of the resin binder, the defects of the problems are very obvious, such as: odor problems, poaching and high temperature cooking performance, composite strength, etc. The common water-based polyurethane ink has poor color development and poor printing performance, can only meet the requirements of common water boiling performance, and has the difficult problem of odor which is difficult to completely solve, and the problems restrict the popularization and application of the water-based ink.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of the ink vehicle, and the ink vehicle prepared by the method has good high-temperature cooking resistance.
The invention also provides the ink binder prepared by the method.
The invention also provides an application of the ink vehicle.
A method of making an ink vehicle according to an embodiment of the first aspect of the invention includes the steps of:
s1, preparation of polyurethane prepolymer:
reacting oligomer polyol and polyisocyanate at 80-90 ℃ for 1.5-2 h, then adding a hydrophilic chain extender dissolved in a solvent to react at 80-90 ℃ for 1.5-2.0 h, and diluting and neutralizing a product to obtain an NCO-terminated polyurethane prepolymer A;
taking the dehydrated hydroxyl-terminated organic silicon resin and polyisocyanate to react for 1.5-2 h at the temperature of 80-90 ℃, adding a hydrophilic chain extender solution dissolved in a solvent to react for 1.5-2.0 h at the temperature of 80-90 ℃, and diluting and neutralizing the product to obtain an NCO-terminated polyurethane prepolymer B;
reacting the dehydrated small molecular weight polyol with isocyanate at 80-90 ℃ for 2-3 h, diluting and neutralizing the product to obtain an NCO-terminated polyurethane prepolymer C;
s2, neutralization and dilution of polyurethane prepolymer:
mixing the NCO-terminated polyurethane prepolymer A and B obtained in the step, cooling to 30-40 ℃ to obtain a polyurethane prepolymer, and adding water to disperse the polyurethane prepolymer to obtain a mixed solution;
s3, post-chain extension and crosslinking of the prepolymer:
and (3) adding the mixed solution obtained in the step (S2) into an aqueous solution containing an amine chain extender under a stirring state for chain extension, then dripping the NCO-terminated polyurethane prepolymer C into the aqueous solution, adding a silane coupling agent for crosslinking reaction, removing the solvent, and then adjusting the solid content with water to obtain the aqueous polyurethane ink binder.
According to some embodiments of the present invention, the oligomer polyol in the step S1 is at least one selected from polyether polyol or polyester polyol having a molecular weight of 1000 to 3000; preferably, the molecular weight of the oligomer polyol is 1500-2500; more preferably, the oligomer polyol has a molecular weight of 1800 to 2000.
According to some embodiments of the present invention, the oligomer polyol is added in an amount of 35 to 45% of the amount of solids in the aqueous polyurethane ink vehicle obtained in step S3.
According to some embodiments of the invention, the polyisocyanate is selected from at least one of an aromatic diisocyanate or an aliphatic diisocyanate.
According to some embodiments of the present invention, the total amount of the polyisocyanate added in step S1 (preferably, the amount of the polyisocyanate added in prepolymer a is 12-20%, the amount of the polyisocyanate added in prepolymer B is 8-16%, the amount of the polyisocyanate added in prepolymer C is 6-10%, and the three are not the maximum at the same time) is 26-35% of the amount of the solid in the aqueous polyurethane ink vehicle obtained in step S3.
According to some embodiments of the invention, the hydrophilic chain extender is selected from at least one of a carboxyl-type chain extender or a sulfonate-type chain extender.
According to some embodiments of the present invention, the hydrophilic chain extender is added in an amount of 5 to 8% of the amount of solids in the aqueous polyurethane ink vehicle obtained in step S3.
According to some embodiments of the invention, the neutralizing operation comprises the step of adding a neutralizing agent selected from at least one of triethylamine, ammonia water or N-methyldiethanolamine.
According to some embodiments of the invention, the neutralizing agent is added in an amount of 85 to 95% neutralization.
According to some embodiments of the invention, the hydroxyl terminated silicone resin has a molecular weight of 2000 to 5000; preferably, the molecular weight of the hydroxyl-terminated organic silicon resin is 2000-3000; more preferably, the molecular weight of the hydroxyl-terminated silicone resin is 2000-2500.
According to some embodiments of the invention, the small molecular weight polyol is a small molecular weight polyol with a side chain structure; preferably, the low molecular weight polyol is selected from at least one of methyl propylene glycol, 3-methyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol.
According to some embodiments of the invention, the amine chain extender is selected from at least one of ethylenediamine, diethylenetriamine, isophoronediamine, diethylenetriamine; the addition amount of the amine chain extender is 3-10% of the solid matter amount in the aqueous polyurethane ink binder obtained in the step S3.
According to some embodiments of the invention, the silane coupling agent is selected from at least one of aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltriethoxysilane; preferably, the adding amount of the silane coupling agent is 1-4% of the solid matter amount in the aqueous polyurethane ink vehicle obtained in the step S3.
According to some embodiments of the invention, the aqueous polyurethane ink vehicle has a solids content of 25 to 32%.
The method provided by the embodiment of the invention has at least the following beneficial effects: the preparation method provided by the embodiment of the invention is simple and convenient to operate, mild in condition, suitable for industrial production, easy to control each parameter, stable in product quality, less in used organic solvent and beneficial to the physical health of workers; the modified waterborne polyurethane synthetic structure is designed, so that the release effect of the polyurethane resin on the solvent and water is improved, the performance requirement of reducing the solvent residue can be met, and the modified waterborne polyurethane synthetic structure can achieve<0.1mg/m2The following (conventional solvent ink 1-20 mg/m)2The index is obviously much higher), can completely meet the requirement of residual solvent of food and medicine packaging products (the index specification of residual solvent of medicine package is highest, and can meet the requirements of all food packaging), meets the performance index requirements of food and medicine, and has good application prospect.
The aqueous polyurethane ink vehicle according to the embodiment of the second aspect of the invention is prepared by the method.
The aqueous polyurethane ink vehicle according to the embodiment of the invention has at least the following beneficial effects: compared with the existing modified polyurethane resin, the waterborne polyurethane in the connecting material of the scheme of the invention has the characteristics of good adhesive force, good re-solubility, high composite strength, capability of being cooked at high temperature and the like; the waterborne polyurethane ink prepared by the waterborne polyurethane resin binder with excellent performance can meet the requirements of high-temperature cooking performance, has excellent printability and composite performance, and has good industrial application prospect.
According to the application of the embodiment of the third aspect of the invention, the ink color paste comprises the aqueous polyurethane ink binder.
According to some embodiments of the present invention, the ink paste further comprises a pigment, an auxiliary agent I, water I and isopropyl alcohol; preferably, the mass ratio of the water-based polyurethane ink binder, the pigment, the auxiliary agent I, the water I and the isopropanol is (30-50): 15-60): 2-10: (10-20): 1-2).
According to some embodiments of the invention, the adjuvant I comprises at least one of a defoamer, a dispersant, a stabilizer and an active agent.
The raw materials for preparing the ink comprise the ink color paste; preferably, the ink is a surface printing ink.
The ink disclosed by the embodiment of the invention has at least the following beneficial effects: the ink prepared by the invention has good state fluidity and excellent color development (the concentration is higher than that of solvent ink), the adhesive force firmness and the composite strength both meet the performance index requirement of product or approach the performance index of the solvent ink composite ink, and the result of a test of high-temperature cooking at 130 ℃ for 30min shows that the composite strength does not obviously change before and after the cooking, the hue of the ink does not obviously change, and the ink meets the requirement of the high-temperature cooking performance.
According to some embodiments of the invention, the raw materials for preparing the ink paste are additionally added with the aqueous polyurethane ink binder; preferably, the addition ratio of the ink color paste to the aqueous polyurethane ink binder is (50-75): (20-40).
According to some embodiments of the present invention, the raw materials for preparing the ink paste further comprise an auxiliary agent II, water II and ethanol, wherein the auxiliary agent II is at least one selected from a defoaming agent, a stabilizer, a leveling agent, a slip agent, an active agent or a mildew inhibitor.
The application of the ink in plastic film printing.
The application of the embodiment of the invention has at least the following beneficial effects: the ink prepared from the binder can meet the performance requirement of high-temperature cooking resistance, and meanwhile, the ink has good printability and composite performance and good application prospect.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The first embodiment of the invention is as follows: a preparation method of a water-based polyurethane ink binder comprises the following preparation steps:
(1) preparing a polyurethane prepolymer:
firstly, mixing oligomer polyol (polyether polyol PPG-2000 with molecular weight of 2000, the addition amount of which accounts for 34 percent of the solid matter amount in the finally obtained aqueous polyurethane ink vehicle) and isophorone diisocyanate (isophorone diisocyanate of Wingchu company), the addition amount of which accounts for 12 percent of the solid matter amount in the finally obtained aqueous polyurethane ink vehicle, reacting for 1h at 90 ℃, then adding a hydrophilic chain extender 2, 2-dimethylolpropionic acid (2,2-bis (hydroxymethyl) propionic acid, DMPA) dissolved in a solvent, the adding amount of the polyurethane prepolymer accounts for 5% of the solid mass in the finally obtained aqueous polyurethane ink binder, the reaction is carried out for 2.0h at 90 ℃, the system is cooled to 50 ℃, then a solvent is added to reduce the viscosity, and finally a neutralizer ammonia water (with the concentration of 24%) is added to neutralize the system until the neutralization degree is 90%, so as to obtain an NCO-terminated polyurethane prepolymer A;
② dehydrating the hydroxyl-terminated organosilicon resin 8807 (silok 8807 of Chorocco chemical Co., Guangzhou), the addition amount of which accounts for 8 percent of the solid matter amount in the finally obtained aqueous polyurethane ink vehicle, for 0.5h under the condition of 110 ℃ and pressure of-0.9 mpa, and then mixing with IPDI (isophorone diisocyanate of Wingchu company); the addition amount of the chain extender DMPA (dimethylolpropionic acid) accounts for 10 percent of the solid matter amount in the finally obtained aqueous polyurethane ink binder, the mixture is reacted for 1.5 hours at 85 ℃, then the hydrophilic chain extender DMPA (dimethylolpropionic acid) dissolved in a solvent is added, the addition amount of the chain extender DMPA accounts for 8 percent of the solid matter amount in the finally obtained aqueous polyurethane ink binder, the reaction time is 2.0 hours at 90 ℃, acetone is added to reduce the viscosity after the system is cooled to 50 ℃, and finally the neutralizing agent triethylamine is added to neutralize the system until the neutralization degree is 95 percent, so that the polyurethane prepolymer B with NCO groups is obtained;
thirdly, adding polyol (2-methylpropanediol) with small molecular weight, which is dehydrated for 0.5h under the condition of 110 ℃ and pressure of-0.9 mpa, into the mixture, wherein the adding amount of the polyol accounts for 5% of the mass of the solid in the finally obtained aqueous polyurethane ink binder, adding isocyanate isophorone diisocyanate into the mixture, wherein the adding amount of the isocyanate accounts for 8% of the mass of the solid in the finally obtained aqueous polyurethane ink binder, reacting the mixture for 2 hours at 85 ℃, cooling the mixture to 50 ℃, adding acetone into the mixture to dilute the mixture to reduce the viscosity, and obtaining the NCO-terminated polyurethane prepolymer C.
(2) Neutralizing and diluting the polyurethane prepolymer:
mixing the NCO-terminated polyurethane prepolymer A and B obtained in the step (1), cooling to 30 ℃, adding deionized water, stirring at a high speed and dispersing for 0.5h to fully disperse the polyurethane prepolymer in water;
(3) and (3) chain extension and crosslinking of the prepolymer:
and (3) slowly adding the aqueous solution obtained in the step (2) into an aqueous solution of an amine chain extender isophorone diamine (the addition amount of isophorone diamine accounts for 8% of the solid matter amount in the finally obtained waterborne polyurethane ink binder) under a stirring state for post chain extension, adjusting the rotating speed to 100 r/min for stirring after chain extension is finished, slowly dripping the polyurethane prepolymer C for about 2h, adding a silane coupling agent N-aminoethyl-3-aminopropyltriethoxysilane (the addition amount accounts for 2% of the solid matter amount in the finally obtained waterborne polyurethane ink binder), heating to 60 ℃ for post crosslinking reaction, and obtaining a semi-finished product of the waterborne polyurethane ink binder.
(4) And (4) heating the semi-finished product obtained in the step (3) to a temperature of negative pressure, extracting the contained solvent, and then adjusting the solid content to 25% by using deionized water to obtain the waterborne polyurethane ink binder.
Mixing the aqueous polyurethane ink binder prepared by the operation with a pigment, an auxiliary agent I (composed of a Foamex 842 defoaming agent, a Dispers 755w dispersing agent, an AMP 95 stabilizing agent and a WET 245 active agent, and mixing the components according to a mass ratio of 0.1:1.5:1: 0.5), water and isopropanol according to a weight ratio of 15-60: mixing the raw materials at a ratio of 30-50: 2-10: 10-20: 1-2 (in the embodiment, the mass ratio is 40:30:2:10:1), and grinding the mixture to a fineness of 10 microns by using a closed sand mill to obtain a color paste for later use.
The prepared color paste is further adjusted into printing ink, the printing ink color paste, the water-based polyurethane printing ink binder, the auxiliary agent II (comprising Surfynol DF 110 defoamer, AMP 95 stabilizer, Dynol 604 leveling agent, W410 slipping agent, WE 3322 active agent and MB-11 mildew preventive which are mixed according to the mass ratio of 1:0.5:1:2:0.5: 0.1), water and ethanol which are mixed according to the ratio of (50-75) to (20-40) to (2-10) to (10-25) to (1-5), after being mixed according to the ratio of 60:30:8:15:4, the mixture is dispersed at high speed (1300 r/min) (the time is usually 30-60 min, depending on the weight of the specific grinding material, the grinding time is 45min), and the grinding (the grinding time is 60-180 min, depending on the weight of the grinding material, the grinding medium can be zirconium oxide or pure zirconium, the grinding time is 120min, grinding the zirconium oxide as a grinding medium), and filtering to finally obtain the finished product of the waterborne polyurethane plastic film composite ink. The finished ink product has good fluidity and excellent color development (the concentration is higher than that of solvent ink), and the adhesive force firmness and the composite strength can both meet the performance index requirement of the product or approach the performance index of the solvent ink composite ink; the test of 30min at 130 ℃ of high-temperature cooking shows that the composite strength is not obviously changed before and after the cooking, the color phase of the ink is not obviously changed, and the high-temperature cooking performance requirement is met. Specifically, the performance of the ink was tested with reference (GB/T26394) and the results are shown in Table 1 below:
TABLE 1
The heavy metal content in the ink is tested, the testing process is carried out according to EN71-3:2013+ A1: 2014-soluble element content (class III: the scratch-able toy material), an inductively coupled plasma emission spectrometer (ICP-OES) is used for analyzing, the testing result does not exceed the limit value of European toy safety standard EN71-3:2013+ A1: 2014-soluble element content, and the specific testing result is shown in the following table 2:
TABLE 2
In the above table, MDL represents the detection limit, and 001 represents the actual detection result.
For Substances meeting the REACH specification of clause 57, called highly concerned Substances (SVHC) for short, the concentration of the test result is less than 0.1% and the test result is qualified, and the test commission of this project is that ICP-OES, UV-VIS, GC-MS, HPLC-DAD/MS are used by SGS standard technical service limited, guangzhou branch company, and all the components are not detected.
Reference is made to 2011/65/EU appendix II modified Instructions (EU)2015/863 for Hazardous components (RoHS) in the inks, in which the cadmium content is determined by ICP-OES, with reference to IEC62321-5: 2013; lead was determined by ICP-OES with reference to IEC62321-5: 2013; the content of mercury is determined by ICP-OES according to IEC62321-4: 2013; the content of the six prices is determined by an ultraviolet-visible spectrophotometer colorimetric method according to IEC62321: 2008; the content of polybrominated biphenyls (PBBs) and polybrominated Diphenyl Ethers (PBDEs) was determined by GC-MS, with reference to IEC62321-6: 2015; phthalate content the phthalate content was determined by GC-MS with reference to EN14372:2004 and it was found that no harmful components were detected.
The same amount of commercially available water-based acrylic resin and the same amount of commonly available water-based polyurethane were prepared into ink under the same conditions by referring to the above-mentioned operations, and the performance of the obtained ink was measured and the results are shown in table 3 below:
TABLE 3
In the above table, the results of wettability, printability, dryness, odor, re-solubility, and solubility are all on a scale, where 1 means poor, 2 is poor, 3 is acceptable, 4 is better, and 5 is excellent.
As can be seen from Table 2, the modified waterborne polyurethane provided by the embodiment of the invention has good adhesion, solubility, composite strength and high-temperature cooking performance.
In addition, comparative tests were also carried out on other different ink formulations with reference to the conventional methods of the prior art, in particular:
comparative scheme 1: aqueous chlorine vinegar scheme
Mixing the prepared aqueous polyurethane ink binder, modified aqueous vinyl chloride-acetate binder (Nissan chemical polyethylene copolymer latex, VINYBLAN 700), water, ethanol, isopropanol, pigment and an auxiliary agent III (composed of Dispers 755W dispersant, Surfynol DF 110 defoaming agent, AMP 95 stabilizer, Dynol 604 flatting agent, W410 slipping agent, WE 3322 active agent and MB-11 mildew preventive according to the mass ratio of 1.5:1:0.5:1:2:0.5: 0.1) according to the weight ratio of 25-60: 5-15: 8-30: 3-10: 1-10: 10-50: 5-15, and specifically, mixing the components in the ratio of 50:10:20:6:5:25:10 in the comparison process to prepare the plastic gravure water-based ink product.
The prepared ink film has the advantages of improving the hardness, improving the adhesion effect of the ink and improving the drying effect, but the compatibility of the binder is poor, the adhesive force of the ink is reduced, the composite strength is also affected, and the placing state of the ink is also poor.
Comparative scheme 2: aqueous polyester protocol
Mixing the prepared aqueous polyurethane ink connecting material, modified polyester connecting material (modified polyester resin of BASF, Joncryl FLX5200), water, ethanol, isopropanol, pigment and auxiliary agent III (composed of Dispers 755W dispersant, Surfynol DF 110 defoaming agent, AMP 95 stabilizer, Dynol 604 flatting agent, W410 slipping agent, WE 3322 active agent and MB-11 mildew preventive according to a mass ratio of 1.5:1:0.5:1:2:0.5: 0.1) according to a ratio of 25-60: 8-30: 3-10: 1-10: 10-50: 5-15, and specifically, mixing the components in the ratio of 50:50:20:6:5:25:10 in the comparison process to prepare the plastic gravure water-based ink product.
The three prepared printing inks are compared, and the results show that the hardness of the ink film prepared by the scheme of the embodiment of the invention is improved, the adhesion effect of the printing ink is improved, the drying effect is improved, but the adhesive force and the composite strength of the printing ink are reduced, and the color development of the printing ink is influenced to a certain extent.
The second embodiment of the invention is as follows: a preparation method of a water-based polyurethane ink binder comprises the following preparation steps:
(1) preparing a polyurethane prepolymer:
adding polyester polyol (synthesized by 3-methyl 1, 5-pentanediol and adipic acid) with oligomer polyol molecular weight of 2000 into 35% of the solid matter in the finally obtained waterborne polyurethane ink binder, and TDI (toluene diisocynate); the adding amount of polyisocyanate accounts for 15% of the solid matter amount in the finally obtained waterborne polyurethane ink binder, mixing and reacting for 1.5h at 80 ℃, then adding a hydrophilic chain extender (DMBA dimethylol butyric acid) dissolved in a solvent, wherein the adding amount of the hydrophilic chain extender accounts for 2.5% of the solid matter amount in the finally obtained waterborne polyurethane ink binder, reacting for 1.5h at 80 ℃, cooling the system to 50 ℃, adding the solvent to reduce the viscosity, and finally adding a neutralizer N-methyldiethanolamine to neutralize until the neutralization degree is 85%, thereby obtaining an NCO-terminated polyurethane prepolymer A;
② hydroxyl-terminated organic silicon resin 1647 (manufacturer: BLUESTAR SILICONES), the adding amount accounts for 5 percent of the solid matter amount in the finally obtained water-based polyurethane ink binder, is dehydrated at 110 ℃, and then is mixed with (aromatic diisocyanate TDI); the addition amount of the chain extender is 10 percent of the solid matter amount in the finally obtained waterborne polyurethane ink binder, the mixture is reacted for 1.5 hours at the temperature of 80 ℃, then the hydrophilic chain extender (DMBA dimethylolbutyric acid) dissolved in the solvent is added, the addition amount of the chain extender is 2.5 percent of the solid matter amount in the finally obtained waterborne polyurethane ink binder, the reaction is carried out for 1.5 hours at the temperature of 80 ℃, the solvent is added to reduce the viscosity after the system is cooled to 50 ℃, and finally the neutralizer (triethylamine) is added to neutralize the system until the neutralization degree is 85 percent, so that the polyurethane prepolymer B with the NCO group at the end is obtained;
mixing the 3-methyl-1, 5-pentanediol polyol with low molecular weight dehydrated at high temperature, the addition amount of which accounts for 5% of the solid matter in the finally obtained waterborne polyurethane ink binder, and the isocyanate TDI, the addition amount of which accounts for 5% of the solid matter in the finally obtained waterborne polyurethane ink binder, reacting for 2 hours at 80 ℃, cooling to 50 ℃, adding a solvent for dilution and reducing viscosity to obtain the NCO-terminated polyurethane prepolymer C.
(2) Neutralizing and diluting the polyurethane prepolymer:
mixing the NCO-terminated polyurethane prepolymer A and B obtained in the step (1), cooling to 30 ℃, adding deionized water, stirring at a high speed and dispersing for 0.5h to fully disperse the polyurethane prepolymer in water;
(3) and (3) chain extension and crosslinking of the prepolymer:
and (3) slowly adding the aqueous solution obtained in the step (2) into an aqueous solution of an amine chain extender (ethylenediamine, the addition amount of the ethylenediamine accounts for 3% of the solid matter amount in the finally obtained aqueous polyurethane ink binder) under a stirring state for post-chain extension, adjusting the rotating speed to 100 r/min and stirring for 1 hour after chain extension is finished, slowly dripping the polyurethane prepolymer C for about 1.5 hours, adding a silane coupling agent (aminopropyltriethoxysilane, the addition amount of the aminopropyltriethoxysilane accounts for 1% of the solid matter amount in the finally obtained aqueous polyurethane ink binder, heating to 60 ℃ for post-crosslinking reaction, and obtaining a semi-finished product of the aqueous polyurethane ink binder.
(4) And (4) heating the semi-finished product obtained in the step (3) to a temperature of negative pressure, extracting the contained solvent, and then adjusting the solid content to a required range (25%) by using deionized water to obtain the aqueous polyurethane ink binder.
The third embodiment of the invention is as follows: a preparation method of a water-based polyurethane ink binder comprises the following preparation steps:
(1) preparing a polyurethane prepolymer:
firstly, taking oligomer polyol (polyester polyol with molecular weight of 2000, prepared from polyester polyol synthesized from methyl propylene glycol and adipic acid), wherein the addition amount of the oligomer polyol accounts for 40% of the solid matter amount in the finally obtained waterborne polyurethane ink binder) and polyisocyanate IPDI; the addition amount of the chain extender accounts for 20% of the solid matter amount in the finally obtained waterborne polyurethane ink binder, the mixture is reacted for 2 hours at 90 ℃, then the hydrophilic chain extender (DMBA dimethylolbutyric acid) dissolved in the solvent is added, the addition amount of the hydrophilic chain extender accounts for 4% of the solid matter amount in the finally obtained waterborne polyurethane ink binder, the reaction is carried out for 2.0 hours at 90 ℃, the solvent is added to reduce the viscosity after the system is cooled to 50 ℃, and finally the neutralizer (N-methyldiethanolamine) is added to neutralize until the neutralization degree is 95%, so that the NCO-terminated polyurethane prepolymer A is obtained;
secondly, dehydrating the hydroxyl-terminated organic silicon resin 8807 (silok 8807 of Choucho chemical Co., Guangzhou) with the addition amount accounting for 10 percent of the solid matter in the finally obtained aqueous polyurethane ink binder at high temperature, and then mixing the dehydrated hydroxyl-terminated organic silicon resin with polyisocyanate IPDI (isophorone diisocyanate, a product of Yingchuang company); the addition amount of the chain extender is 13 percent of the solid matter amount in the finally obtained waterborne polyurethane ink binder, the mixture is reacted for 2 hours at the temperature of 90 ℃, then the hydrophilic chain extender (DMBA dimethylolbutyric acid) dissolved in butanone is added, the addition amount of the chain extender is 4 percent of the solid matter amount in the finally obtained waterborne polyurethane ink binder, the reaction is carried out for 2.0 hours at the temperature of 90 ℃, the system is cooled to 50 ℃, then the solvent is added to reduce the viscosity, finally the neutralizer (N-methyldiethanolamine) is added to neutralize the mixture until the neutralization degree is 85 percent, and the polyurethane prepolymer B with the NCO group at the end is obtained;
mixing 3 percent of polyol 3-methyl 1, 5-pentanediol with small molecular weight dehydrated at high temperature and 3 percent of the solid matter in the finally obtained waterborne polyurethane ink binder with 6 percent of the addition of diisocyanate IPDI (isophorone diisocyanate of Wingchuang company), reacting for 3 hours at 90 ℃, cooling to 50 ℃, adding a solvent to dilute and reduce viscosity, and obtaining the NCO-terminated polyurethane prepolymer C.
(2) Neutralizing and diluting the polyurethane prepolymer:
mixing the NCO-terminated polyurethane prepolymer A and B obtained in the step (1), cooling to 40 ℃, adding deionized water, stirring at a high speed and dispersing for 0.5h to fully disperse the polyurethane prepolymer in water;
(3) and (3) chain extension and crosslinking of the prepolymer:
and (2) slowly adding the aqueous solution obtained in the step (2) into an aqueous solution of an amine chain extender (isophorone diamine, the addition amount of which accounts for 5% of the solid matter amount in the finally obtained aqueous polyurethane ink binder) under a stirring state for post chain extension, adjusting the rotating speed to high-speed stirring after chain extension is finished, slowly dripping the polyurethane prepolymer C for about 2 hours, adding silane coupling agents (aminopropyltriethoxysilane and N-aminoethyl-3-aminopropyltriethoxysilane in a mass ratio of 1:1, the addition amount of which accounts for 4% of the solid matter amount in the finally obtained aqueous polyurethane ink binder) after dripping is finished, heating to 60 ℃ for post crosslinking reaction, and obtaining a semi-finished product of the aqueous polyurethane ink binder.
(4) And (4) heating the semi-finished product obtained in the step (3) to a temperature of negative pressure, extracting the contained solvent, and then adjusting the solid content to a required range (25-32%) by using deionized water to obtain the aqueous polyurethane ink binder.
The pigment used in the ink can be specifically adjusted according to the requirement, and the common pigment types are as follows:
TABLE 4
| Printing ink | Name of pigment used | Pigment index number | CAS number |
| White ink | Titanium white powder | C.I.PigmentWhite 6 | 13463-67-7 |
| Yellow ink | Permanent yellow G | C.I.PigmentYellow 14 | 5468-75-7 |
| Red ink | Permanently magenta FBB | C.I.PigmentRed 146 | 5280-68-2 |
| Blue ink | Phthalocyanine blue | C.I.PigmentBlue 15:3 | 147-14-8 |
| Black ink | Carbon black | C.I.PigmentBlack 7 | 133-86-4 |
The invention designs a novel modified polyurethane ink binder which is used for preparing a polyurethane prepolymer A, a prepolymer B and a prepolymer C respectively, so that the instability among batches caused by the reaction of various polyols and polyisocyanates is avoided, and particularly, the synthesized organic silicon resin prepolymer B is neutralized firstly and then mixed with the prepolymer A for water hydration because the compatibility of the synthesized organic silicon resin prepolymer B with other prepolymers is poor; the organic silicon chain segment with poor water solubility is creatively introduced into the molecular structure of the waterborne polyurethane, so that the coating film can have good tolerance after being dried; in the chain extension stage, amines are used for carrying out primary chain extension, and then the prepolymer component C of the NCO group is used for carrying out final chain extension, so that the whole chain extension process is stable and controllable, and the problem that the resin is separated out from water and fails due to the fact that the water solubility is poor because the molecular weight rises too fast in the chain extension process is avoided; the problems of drying and re-dissolving are solved creatively by using various neutralizers, and the use requirements of the waterborne polyurethane resin in the whole printing and drying process can be met by using the physical characteristics of different neutralizers with different volatilization speeds; finally, the coupling agent is added into the resin and heated to 60 ℃ for reaction and curing, so that the coupling agent can be ensured to exist in the resin stably and finally, the physical property of the resin in the storage process can not be changed.
The ink redissolution prepared by the binder disclosed by the embodiment of the invention is obviously superior to the water-based ink in the prior art, the water-based ink in the prior art has the problem of redissolution, so that long-time printing faults (such as dry plate, blocked plate, skip printing, dirty plate, hairspring, and the like) are caused, and the product quality and the production efficiency are influenced. The excellent re-solubility of the embodiment of the invention is mainly controlled by three aspects:
firstly, the crosslinking degree and the molecular weight of resin molecules are controlled in the synthesis process, the solvent release property of the resin is reduced due to the excessively high crosslinking degree and molecular weight, the strength of the resin is reduced and the solvent resistance is reduced due to the excessively low crosslinking degree and molecular weight, and the proper crosslinking degree and molecular weight need to be determined through a large amount of experiments.
And (II) properly introducing polyester polyol or micromolecular polyol containing long carbon chain side groups into the main chain structure can increase the water and alcohol release performance of the polyurethane resin, but the proportion of ether bonds and water-soluble groups is properly reduced, and a better alcohol and water release effect can be obtained, but the water and alcohol release performance is too good, so that the water and alcohol solubility of the whole polyurethane resin is possibly poor, and the polyurethane resin can be controlled in a better range by adopting the scheme of the invention.
And thirdly, a plurality of water-soluble groups are used together in the molecular structure of the polyurethane to solve the problem of poor re-solubility. For example, the water-based self-emulsifying capability of the polyether segment can be used as an auxiliary under the premise that the carboxylate group provides water solubility, and the water solubility can be provided by the partial structure polyether structure when partial neutralizing agent volatilizes to cause the water solubility of the whole resin to be reduced.
The ink prepared by the binder disclosed by the embodiment of the invention also has excellent adhesion and composite properties, is suitable for printing common plastic film substrates, has good temperature resistance and water resistance, can be used for high-temperature cooking (135 ℃) performance and application, is suitable for various composite structures, and can meet the requirement that one ink can correspond to multi-purpose integrated ink. The polyurethane prepared by the embodiment of the invention has an especially excellent adhesion firmness effect due to the structure, so that the resin liquid is suitable for the requirements of surface printing ink products. The polyurethane ink has good composite ink, and the surface printing application can be carried out by adding a carbodiimide curing agent to carry out double-liquid treatment, so that the temperature resistance, the adhesive force, the scratch property and the water boiling property of the ink are improved, the performance requirements of the conventional surface printing ink can be met, and the polyurethane ink is applied to surface printing packaging products. The carbodiimide curing agent has good water solubility and stability, has no obvious reaction at normal temperature, but further has crosslinking reaction with the modified waterborne polyurethane along with the volatilization of solvent/moisture, can generate a resin structure with large molecular weight, and further enhances the adhesive force, scratch resistance and temperature-resistant poaching performance.
The water-based polyurethane resin as the main material of the printing ink starts from the structural design, the molecular structure has good wettability (such as a high-polarity resin structure, a low-surface-energy main chain and various branched chain structures) and is matched with a dispersing agent, so that the good wetting and spreading, surface polarity and adhesion effect of the resin on a base material are ensured, and the adhesion force of the printing ink achieves a good effect; the scheme of the invention introduces more polar groups into a molecular mechanism, improves the number of hydrogen bonds of polyurethane, keeps a certain number of crystalline chain segment structures, can also improve the composite strength, and simultaneously can consider that the molecular structure of ink resin is designed to be similar to the molecular structure of polyurethane glue used in cooperation so as to improve the composite strength.
The ink prepared by the binder provided by the embodiment of the invention also has excellent solubility, the novel modified polyurethane water-based resin can meet the requirement of pure water solubility and the requirement of good alcohol solubility, and the ink can meet the requirements of dilution solvents with different alcohol/water ratios and can obtain good printing performance; particularly, the printing ink has good alcohol solubility, and can only adjust the alcohol/water ratio to achieve good ink spreading effect and printing effect aiming at the existing equipment in domestic markets and partial base materials with poor treatment degree, such as PE, CPP, SPP, POF and the like, due to the limitation of application, so that high requirements are provided for the solubility of different alcohol/water ratios of the ink. The water solubility and alcohol solubility of the embodiments of the present invention are controlled by the following aspects:
water solubility: the water solubility can be remarkably improved by increasing the content of soluble groups, such as ether bonds, sulfonate groups or carboxylate groups in the main chain, while too high a content of water-soluble groups reduces the water resistance after film formation; according to the invention, by designing a reasonable molecular structure and utilizing process control to distribute soluble groups in the whole polyurethane molecule more uniformly, the degradation of performances such as water resistance, solvent resistance and the like after film formation can be avoided while good water solubility is maintained.
(di) alcohol solubility: firstly, the polarity of polyol used for polyurethane synthesis is considered, polyether polyol is used for replacing polyester polyol to synthesize polyurethane, the resin alcohol solubility can be obviously improved, secondly, the crystallinity of a polyurethane chain segment can be properly reduced, and the crystallinity of polyester and polyether polyol in a polyurethane structure can be damaged by selecting micromolecular polyol with a side chain structure for chain extension, so that the solubility is improved.
A, B and C in the end-NCO-group polyurethane prepolymer A, the end-NCO-group polyurethane prepolymer B and the end-NCO-group polyurethane prepolymer C do not represent the sequence, and the three prepolymers can be prepared simultaneously or the preparation sequence can be changed randomly only for the convenience of distinguishing. The same auxiliaries I and II, I and II, do not represent a sequential order or necessarily differ from one another, but merely for the sake of illustration.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (6)
1. A preparation method of a water-based polyurethane ink binder is characterized by comprising the following steps: the method comprises the following steps: s1, preparation of polyurethane prepolymer:
s11, reacting oligomer polyol with polyisocyanate at 80-90 ℃ for 1.5-2 h, then adding a hydrophilic chain extender dissolved in a solvent to react at 80-90 ℃ for 1.5-2.0 h, and diluting and neutralizing the product to obtain an NCO-terminated polyurethane prepolymer A;
s12, taking the dehydrated hydroxyl-terminated organic silicon resin to react with polyisocyanate for 1.5-2 h at 80-90 ℃, adding a hydrophilic chain extender solution dissolved in a solvent, reacting for 1.5-2.0 h at 80-90 ℃, and diluting and neutralizing the product to obtain an NCO-terminated polyurethane prepolymer B;
s13, reacting the dehydrated small molecular weight polyol with isocyanate at 80-90 ℃ for 2-3 h, diluting and neutralizing the product to obtain an NCO-terminated polyurethane prepolymer C;
s2, neutralization and dilution of polyurethane prepolymer:
mixing the NCO-terminated polyurethane prepolymer A and B obtained in the step, cooling to 30-40 ℃ to obtain a polyurethane prepolymer, and adding water to disperse the polyurethane prepolymer to obtain a mixed solution;
s3, post-chain extension and crosslinking of the prepolymer:
adding the mixed solution obtained in the step S2 into an aqueous solution containing an amine chain extender under a stirring state for chain extension, then dripping the NCO-terminated polyurethane prepolymer C into the aqueous solution, adding a silane coupling agent for crosslinking reaction, removing the solvent, and adjusting the solid content with water to obtain the aqueous polyurethane ink binder;
the oligomer polyol in the step S11 is polyether polyol PPG-2000;
the molecular weight of the polyether polyol PPG-2000 is 2000;
the addition amount of the oligomer polyol in the step S11 accounts for 34% of the solid matter amount in the finally obtained aqueous polyurethane ink vehicle;
the polyisocyanate in the step S11 is isophorone diisocyanate of winning companies;
the adding amount of the polyisocyanate in the step S11 accounts for 12% of the solid matter amount in the finally obtained aqueous polyurethane ink vehicle;
in the step S11, the hydrophilic chain extender is 2, 2-dimethylolpropionic acid;
in the step S11, the adding amount of the hydrophilic chain extender accounts for 5% of the solid matter amount in the finally obtained aqueous polyurethane ink vehicle;
the hydroxyl-terminated silicone resin in step S12 is silok 8807 from siloco chemical ltd, guangzhou;
the adding amount of the hydroxyl-terminated organic silicon resin in the step S12 accounts for 8% of the solid matter amount in the finally obtained aqueous polyurethane ink binder;
the polyisocyanate in the step S12 is isophorone diisocyanate of winning companies;
the adding amount of the polyisocyanate in the step S12 accounts for 10% of the solid matter amount in the finally obtained aqueous polyurethane ink vehicle;
in the step S12, the hydrophilic chain extender is 2, 2-dimethylolpropionic acid;
the adding amount of the hydrophilic chain extender in the step S12 accounts for 8% of the solid matter amount in the finally obtained aqueous polyurethane ink vehicle;
in step S13, the small molecular weight polyol is 2-methyl propylene glycol;
the addition amount of the small molecular weight polyol in the step S13 accounts for 5% of the solid matter amount in the finally obtained aqueous polyurethane ink vehicle;
in the step S13, the isocyanate is isophorone diisocyanate;
the adding amount of the isocyanate in the step S13 accounts for 8% of the solid matter amount in the finally obtained waterborne polyurethane ink vehicle;
in the step S3, the amine chain extender is isophorone diamine;
the adding amount of the amine chain extender in the step S3 accounts for 8% of the solid matter amount in the finally obtained aqueous polyurethane ink binder;
in the step S3, the silane coupling agent is N-aminoethyl-3-aminopropyltriethoxysilane;
the amount of the silane coupling agent added in the step S3 accounts for 2% of the solid content of the finally obtained aqueous polyurethane ink vehicle.
2. The water-based polyurethane ink binder is characterized in that: the aqueous polyurethane ink vehicle is prepared by the method of claim 1.
3. An ink paste, which is characterized in that: the preparation raw materials of the ink paste comprise the aqueous polyurethane ink binder as defined in claim 2.
4. An ink, characterized by: the preparation raw materials of the ink comprise the ink color paste as claimed in claim 3.
5. The ink of claim 4, wherein: the ink is surface printing ink.
6. Use of the ink according to claim 4 or 5 for printing on plastic films.
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