CN109762396B - Water-based ink and preparation method and application thereof - Google Patents
Water-based ink and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to water-based ink which comprises a connecting base material, a modified inorganic pigment, a cosolvent, a foam inhibitor, a stabilizer, an emulsifier, a wetting agent, an antioxidant, a penetrating agent, polyethylene wax and deionized water, and also relates to a preparation method and application of the water-based ink. The water-based ink has excellent multiple performances through unique component selection and mutual cooperation and unique preparation steps, so that the water-based ink can be applied to the technical field of printing, for example, can be applied to multiple specific applications such as advertisement printing, PVC film printing and paper printing, and has good application prospect and popularization potential.
Description
Technical Field
The invention relates to ink and a preparation method and application thereof, in particular to water-based ink and a preparation method and application thereof, belonging to the technical field of fine chemical engineering, especially printing.
Background
With the advancement of science and technology and the increasing printing requirements, higher and higher requirements are put forward on the aspects of ink quality, performance, environmental protection and the like.
As for the ink used for printing, the ink is mainly a solvent-based ink in the early stage, but the ink has serious defects, such as the existence of heavy metals (causing serious pollution to the environment), a large amount of organic volatile matters (especially aromatic compounds such as benzene, toluene and xylene, and volatile matters such as esters and ketones), and the like, which cause serious harm to the environment and printing operators, and the use of the ink is prohibited in a plurality of countries or regions at present.
In order to overcome these drawbacks, researchers have developed aqueous inks (also called water-based inks), which generally use an aqueous resin (or high molecular polymer) as a binder, a dye or pigment as a color base, deionized water as a main solvent (sometimes containing a small amount of organic cosolvent), because the solvent is mainly deionized water and does not contain a large amount of organic solvent in solvent-based ink, therefore, the printing ink has the advantages of safety, environmental protection, organic property and the like, is widely used in flexible printing, gravure printing, silk screen printing and the like at present, is widely popularized and applied in various fields such as toy products for children, cigarette and wine packaging, clothing packaging, food packaging, corrugated paper packaging, toilet paper (sanitary towel) packaging, label paper printing, wallpaper printing and the like, and increasingly embodies the application potential of completely replacing solvent-based ink.
However, aqueous inks have some disadvantages such as poor storage stability, adhesion, etc., and therefore, in order to overcome these disadvantages and to develop a novel aqueous ink, a great deal of intensive research has been conducted on the selection of the overall components of the aqueous ink or the improvement of a specific component thereof, and results have been obtained, for example:
CN101353499A discloses a method for preparing a styrene-acrylic core-shell emulsion linking agent for water-based ink, which comprises a monomer consisting of polymerizable unsaturated acid (such as acrylic acid, methacrylic acid and itaconic acid) accounting for 3.0-8.0% of the weight of the monomer, acrylic ester (such as methyl acrylate, ethyl acrylate, butyl acrylate and isooctyl acrylate) accounting for 42.0-77.0% of the weight of the monomer and styrene accounting for 20.0-50.0% of the weight of the monomer, an emulsifier consisting of polymerizable polyurethane surfactant which accounts for 10.0-20.0% of the weight of the monomer and is prepared by a specific method, water accounting for 1-2 times of the weight of the monomer, and persulfate initiator accounting for 0.2-0.8% of the weight of the monomer, and the styrene-acrylic core-shell emulsion linking agent for water-based ink is obtained by a specific emulsion polymerization method which adopts pre-emulsification process, seed emulsion polymerization and continuous dropwise addition process. The emulsion connecting agent is core-shell emulsion with polyurethane as a shell and styrene-acrylic resin as an inner core, and is used for preparing water-based ink with high glossiness, high wear resistance and high water resistance.
CN101519557A discloses a multifunctional water-based ink, which comprises the following components in parts by weight: 25-35% of water-soluble acrylic resin, 10-20% of pigment, 3-10% of silicon oxide, 15-25% of water, 5-15% of cosolvent, 5-10% of neutralizer, 1-3% of emulsifier, 0.2-1% of defoaming agent, 5-9% of dispersant, 0.2-1% of antistatic agent and 0.1-1% of mildew preventive. The water-based ink is a novel printing water-based ink which is non-toxic, tasteless, waterproof, mildew-proof, antistatic and the like, and has the advantages of simple process and low comprehensive price.
CN101591410A discloses a preparation method of a core-shell type polyurethane/tertiary vinegar emulsion linking agent for water-based ink, which is characterized in that vinyl acetate accounting for 45.0-82.0% of the weight of a monomer and vinyl versatate accounting for 20.0-50.0% of the weight of the monomer form the monomer, polymerizable polyurethane surfactant accounting for 5.0-20.0% of the weight of the monomer and prepared by a specific method forms an emulsifier, water accounting for 1-2 times of the weight of the monomer and persulfate initiator accounting for 0.2-0.8% of the weight of the monomer are adopted, and the core-shell type polyurethane/tertiary vinegar emulsion linking agent for the water-based ink is obtained by a specific emulsion polymerization method adopting a pre-emulsification process, a seed emulsion polymerization process and a continuous dropping process. The emulsion connecting agent for the water-based ink is core-shell emulsion with polyurethane as a shell and tertiary vinegar resin as an inner core, can be used for preparing the water-based ink, and can obtain the water-based ink with high glossiness, high wear resistance and high water resistance.
CN101705030A discloses a preparation method of gravure water-based ink, which comprises the following steps: firstly, mixing and stirring acrylic acid, styrene, vinyl acetate, water, an emulsifier and an initiator uniformly to obtain acrylic acid-styrene-vinyl acetate ternary copolymer emulsion interpenetrating network type water-soluble resin; then placing the acrylic acid-styrene-vinyl acetate ternary copolymer emulsion interpenetrating network type water-soluble resin, pigment, water, isopropanol, ethanol, a defoaming agent, a wetting agent, a flatting agent, a dispersing agent, a coupling agent and an antibacterial agent into an ink mixing barrel for stirring treatment to form pasty ink material; and (3) putting the pasty ink material into a three-roller ink rolling machine for ink rolling to completely crush the pigment particles and uniformly disperse the pigment particles into the liquid binder to prepare the gravure water-based ink. The method has simple process, and the prepared ink has good printability, wet-friction resistance, high gloss and good adhesive force, and can be used for different types of paper.
CN10224345A discloses an environment-friendly emulsion for water-based ink and a preparation method thereof. The emulsion is obtained by the following method: taking ethyl acrylate and methacrylic acid as comonomers, persulfate as an initiator and tert-dodecyl mercaptan as a chain transfer agent, and polymerizing in a water phase to obtain water-soluble resin; then, styrene, acrylate, methacrylate, methacrylic acid, acrylic acid and functional monomers are selected as comonomers, the water-soluble resin in the previous step is used as a protective colloid, a small amount of emulsifier is added, persulfate is used as an initiator, and an emulsion polymerization preparation process is adopted. The prepared emulsion is mainly characterized by integrating the advantages of the water-soluble resin and the acrylic emulsion. The product is used as a binder of the water-based ink and has the advantages of good leveling property, low viscosity, high gloss, quick drying, high adhesion, pollution resistance, adhesion resistance, salt resistance, water resistance, alkali resistance, alcohol dilution resistance and good wear resistance.
CN103613999A discloses a water-based ink, which comprises the following components in parts by weight: 25-30 parts of water-soluble acrylic resin; 6-9 parts of maleic rosin modified acrylic resin; 20-22 parts of water; 10-12 parts of ethanol; 6-8 parts of triethylamine; 20-25 parts of pigment; 2-2.5 parts of an auxiliary agent; the water-based ink is environment-friendly, low in production cost, high in production efficiency, capable of realizing instant drying, free of powder spraying, stable in product, uniform in dispersion and good in using effect, and can be widely applied to printing ink for food packaging.
CN104558377A discloses a resin for water-based ink, a preparation method and an application thereof, wherein the water-based ink comprises the following components in percentage by weight: 0.5-30% of pigment colorant, 0.5-10% of resin for water-based ink, 5-20% of wetting agent, 0.5-20% of penetrating agent, 5-15% of dissolving stabilizer and the balance of deionized water. The resin for the water-based ink is a polymer microparticle emulsion which is prepared by taking an alkali soluble high molecular polymer as an emulsifier and copolymerizing free radical polymerization monomers in a semi-continuous emulsion manner in the presence of a water-soluble peroxide initiator, wherein the polymer microparticle emulsion has the particle size of 50-180nm, the acid value of 30-100mg KOH/g and the glass transition temperature Tg of-50 ℃. The viscosity of the ink changes little with temperature, the nozzle is not blocked, the ink is suitable for printing on glossy paper and common printing paper, and the printed product has clear images, good glossiness, excellent storage stability and scratch resistance.
CN104629531A discloses a nano-alumina modified composite water-based ink, which comprises nano-alumina modified water-based acrylic resin, water-based polyester resin, water, ethanol, pigment, a defoaming agent, a dispersing agent, a leveling agent and a buffering agent. And then preparing the nano aluminum oxide modified waterborne acrylic resin from an alkyl acrylate monomer, a hydroxyalkyl acrylate monomer, silane coupling agent modified inorganic nano particles, polyethylene glycol, a water-soluble initiator, an emulsifier and water. And finally, preparing the nano-alumina modified composite water-based ink from the nano-alumina modified water-based acrylic resin, the water-based polyester resin, water, ethanol, a pigment, an antifoaming agent, a dispersing agent, a leveling agent and a buffering agent. The water-based ink has excellent wear resistance and chemical resistance.
CN104672982A discloses a preparation method of environment-friendly water-based ink. A preparation method of environment-friendly water-based ink is characterized in that organic pigment, resin, deionized water, dimethyl ethanolamine, wetting agent, emulsifier, slow-drying agent, defoaming agent and dispersing agent are added according to a certain proportion and are firstly dispersed in a stainless steel pot; the color paste formula is as follows: 33.5% of resin liquid, 30% of deionized water, 0.3% of dimethylethanolamine, and a dispersant: 0.1 percent of wetting agent, 0.2 percent of emulsifying agent, 0.5 percent of slow-drying agent, 0.2 percent of defoaming agent and 35 percent of organic pigment; the above materials were mixed and stirred for about 1.5 hours, and then stored for 12 hours to allow them to sufficiently react chemically. Due to the adoption of the technical scheme, the product manufactured by the process is suitable for coated paper printing, plastic printing, double-PE paper cup printing, all milk bag printing and napkin printing of high-speed screen lines and high-speed printers; the color is bright and fine; the color is fast and is not easy to fade; resisting alcohol; water proofing and freeze proofing; the wear-resistant effect is good.
CN105482545A discloses a preparation method of a water-based ink binder, which comprises the steps of firstly crushing rosin, putting the crushed rosin into a container, introducing protective gas, heating to melt the rosin, stirring and cooling to 163 ℃ of 160-; then crushing the resin, dissolving the resin in isopropanol, ethylene glycol ethyl ether and ethanol at 40-50 ℃, heating to 70-75 ℃, adding monoethanolamine, keeping the temperature for 3-4 hours, and adjusting the viscosity to be moderate by water; and slowly dropwise adding acrylic acid, styrene, esters and an emulsifier, adjusting with ammonia water, heating to 65-75 ℃, adding ammonium persulfate in the heat-preservation reaction, and heating for the heat-preservation reaction to obtain the binder of the water-based ink. The ink prepared by the binder has better water solubility, stronger tinting strength, stronger stability and the like.
As mentioned above, a great number of water-based inks are disclosed in the prior art, but there is still a need for continued research and improvement of new water-based inks, which is the focus and emphasis of research in the field of water-based inks, and is the basis for the present invention.
Disclosure of Invention
In order to develop a novel water-based ink, a preparation method and a use thereof, the present inventors have conducted a great deal of intensive research and, after a great deal of creative work, have obtained a novel water-based ink, a preparation method and a use thereof.
The invention mainly relates to water-based ink and a preparation method and application thereof.
Further, the present invention is mainly directed to the following aspects.
In a first aspect, the present invention relates to an aqueous ink comprising a linking base, a modified inorganic pigment, a co-solvent, a foam inhibitor, a stabilizer, an emulsifier, a wetting agent, an antioxidant, a penetrant, a polyethylene wax, and deionized water.
It is to be noted that, in the description of the aqueous ink of the present invention, unless otherwise specified, "including" (above and below) referring to the composition includes both open-ended "including", and the like, and closed-ended "consisting of …" and the like, and the like.
In the water-based ink, the water-based ink comprises the following components in parts by mass:
further, the water-based ink comprises the following components in parts by mass:
in the water-based ink of the invention, the connecting base material is prepared according to the following steps:
a1: preparing a pre-polymerization emulsion, specifically:
at room temperature, adding a mixture of 1 part of glycidyl methacrylate and 1.5 parts of vinyl propionate into 10 parts of deionized water according to parts by mass, adding 0.1 part of nonionic surfactant, and fully stirring to obtain a pre-polymerization emulsion;
a2: preparing an initiating solution, specifically:
adding 0.04-0.06 part of initiator and 0.4 part of sodium dodecyl benzene sulfonate into 5 parts of absolute ethyl alcohol by mass part, and fully stirring to obtain a uniform initiating solution;
a3: preparing a polymerization solution, specifically:
respectively weighing 100 parts of the pre-polymerization emulsion and 3 parts of the initiating solution by mass, then dropwise adding 2/3 parts of the initiating solution (namely 2 parts of the initiating solution) into 100 parts of the pre-polymerization emulsion at 50 ℃ under stirring, stopping dropwise adding to obtain a mixed solution, heating the mixed solution to 75 ℃ at a heating rate of 1-5 ℃/min, most preferably at a heating rate of 3 ℃/min, then 5 parts of polytetrahydrofuran diol, 0.06-0.12 parts of a chain extender and the remainder 1/3 of the initiation solution (i.e., 1 part of the initiation solution) were added dropwise simultaneously to the mixture at that temperature, after the three substances are all dripped, the temperature is raised to 85 ℃, the reaction is continued for 50 to 60 minutes, and the high-speed shearing is carried out at the speed of 1000rpm until the emulsification is uniform, thus obtaining the connecting base material.
In the step a1, the nonionic surfactant is a nonionic surfactant having an HLB value of 8.0 ± 0.5, and is specifically selected from any one of polyoxypropylene mannitol trioleate (e.g., Atlas G-2800), tetraethylene glycol monostearate, tetraethylene glycol monooleate, or polyoxypropylene stearate (e.g., Atlas G-3608), and tetraethylene glycol monostearate is most preferably selected.
Wherein, in the step A2, the initiator is dicyclohexyl peroxydicarbonate.
Wherein, in the step a3, the chain extender is a glycol compound, such as diethylene glycol or triethylene glycol, and is most preferably triethylene glycol.
The inventors have found that the step-wise addition of the initiator and the selection of the temperature-increasing rate in step a3 can achieve the best technical effect, because the step-wise addition of the initiator can produce the best initiating effect in different polymerization stages (initial polymerization and chain extension reaction), and the temperature-increasing rate can be selected for further optimal subsequent polymerization after the initial polymerization is completed, thereby affecting the subsequent chain extension reaction.
In the water-based ink of the present invention, the modified inorganic pigment is prepared by the following steps:
b1: grinding the inorganic pigment for many times until the granularity is less than or equal to 5 mu m, then adding the inorganic pigment into 10wt% of polyethylene glycol 200 aqueous solution, and fully stirring to obtain suspension; adding a sodium bicarbonate aqueous solution with the molar concentration of 0.8mol/L into an aqueous solution with the methacrylic acid content of 10wt%, and fully stirring to obtain a mixed solution;
b2: adding ammonium persulfate into the mixed solution, stirring completely, heating to 50 ℃, dropwise adding the suspension in nitrogen atmosphere at the temperature, heating to 65 +/-2 ℃ after dropwise adding, keeping the temperature for reaction for 30-40 minutes, filtering while hot after the reaction is finished, washing the filtrate with absolute ethyl alcohol, fully washing with deionized water until the eluate is neutral, and finally completely drying in vacuum to obtain the modified pigment.
In step B1, the inorganic pigment may be, for example, iron blue, lead chrome yellow, cobalt blue, iron oxide brown, ultramarine, etc., which are well-known inorganic pigments, commercially available, and will not be described in detail.
Wherein, in the step B1, the mass ratio of the inorganic pigment to the polyethylene glycol 200 in the aqueous solution of the polyethylene glycol 200 is 1.2-1.6: 1.
Wherein, in the step B1, the molar ratio of the methacrylic acid to the sodium bicarbonate is 1: 0.1-0.14.
In step B2, the mass ratio of the ammonium persulfate to the methacrylic acid in the mixed solution is 0.2-0.3: 100.
In the step B2, the mass ratio of the mixed liquid to the suspension is 1: 1-2.
The inventors have found that when the inorganic pigment is so modified, the properties of the aqueous ink can be further improved, which should be so modified that the surface of the inorganic pigment is more easily bonded to the oleophilic printing substrate, thereby improving its adhesive strength, and is particularly suitable for printing on hydrophobic substrates.
In the aqueous ink of the present invention, the cosolvent is a glycerol ether compound, specifically, any one of allyl glycidyl ether, ethylene glycol diglycidyl ether, bisphenol a glycidyl ether, and triethylene glycol diglycidyl ether, and is most preferably triethylene glycol diglycidyl ether.
In the water-based ink of the present invention, the foam inhibitor is any one of an ester compound, an alkanol, a multi-branched alkynol, or an ether compound, specifically may be any one of tributyl phosphate, n-decanol, n-dodecanol, polyoxypropylene polyoxyethylene glyceryl ether, and 2,5,8, 11-tetramethyl-6-dodecene-5, 8-diol, and is most preferably a multi-branched alkynol compound 2,5,8, 11-tetramethyl-6-dodecene-5, 8-diol.
In the aqueous ink of the present invention, the stabilizer is any one of tris (nonylphenyl) phosphite, 2, 6-di-tert-butyl-p-cresol, or 4, 4-butylene-bis (3-methyl-6-tert-butylphenol), and most preferably 4, 4-butylene-bis (3-methyl-6-tert-butylphenol).
In the aqueous ink of the present invention, the emulsifier is any one of sodium hexadecylbenzene sulfonate, lauric acid monoglyceride, sucrose ester triglycerol monostearate, sorbitan tristearate, and the like.
In the water-based ink, the wetting agent is perfluoroalkyl polyoxypropylene polyoxyethylene etherThe structural formula is CnF2n+1O(C3H6O)x(C2H4O)yR, wherein n is an integer between 6 and 10, most preferably 8, and x and y are integers between 6 and 10, 14 and 20, respectively. It should be noted that the values for x and y are not absolute integers, but mean average chain lengths, which are conventional definitions and characterization methods in the polymer field and will not be described in detail herein.
The inventors have found that the best results are achieved when n is 8, which should be the case when the long and short perfluorinated chains have the most suitable hydrophobic bonding properties and enable the polyoxyethylene and polyoxypropylene chains to have the best hydrophilic spreading properties (enabling more intimate bonding to the print substrate) in the overall hydrophilic environment of the ink, resulting in the best wetting effect.
The wetting agent is a well known class of polyether compounds, commercially available from a variety of sources, and will not be described in detail herein.
In the water-based ink, the antioxidant is a mixture of isooctyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylate and N, N-bis (2, 4-diaminodiphenyl ether) imine in a mass ratio of 1:1.
In the water-based ink, the penetrant is diisooctyl maleate sodium sulfonate.
In the aqueous ink of the present invention, the polyethylene wax is a very well known substance, and is commercially available from various sources, and will not be described in detail herein.
In a second aspect, the present invention also relates to a process for the preparation of said aqueous ink, said process comprising the steps of:
s1: weighing each component according to the respective mass content;
wherein the linking binder and the modified inorganic pigment are prepared according to the above steps A1-A3 and B1-B2, respectively;
s2: adding a connecting base material, a modified inorganic pigment, a cosolvent, a foam inhibitor, a stabilizer, a wetting agent and an emulsifier accounting for 80 percent of the total amount into deionized water at 40 ℃, and shearing and dispersing at the speed of 1000-1400rpm for 20-30 minutes to obtain a mixture;
s3: adding an antioxidant, a penetrating agent, polyethylene wax and the rest emulsifier accounting for 20 percent of the total amount into the mixture, heating to 50 ℃, continuing to shear and disperse for 40-50 minutes at the speed of 1000-1400rpm, and sanding for many times until the fineness of the ink is less than or equal to 10 microns to obtain the water-based ink.
The inventors have found that when the emulsifier is added in portions, the best emulsion stability can be obtained, and thus the storage stability can be further extended.
In a third aspect, the present invention relates to the use of said aqueous ink in the printing field.
The water-based ink disclosed by the invention has excellent multiple performances, so that the water-based ink can be applied to the technical field of printing, for example, can be applied to multiple specific applications such as advertisement printing, PVC film printing and paper printing, and has good application prospects and popularization potentials.
As described above, the invention provides the water-based ink, the preparation method and the application thereof, and the water-based ink has good properties through the preferable selection and mutual cooperation of a plurality of components and the special treatment of certain unique components, thereby having good application prospect and industrial production potential in the printing field.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
Preparation example 1: preparation of the jointing base
A1: preparing a pre-polymerization emulsion, specifically:
at room temperature, adding a mixture of 1 part of glycidyl methacrylate and 1.5 parts of vinyl propionate into 10 parts of deionized water according to parts by mass, adding 0.1 part of nonionic surfactant tetraethylene glycol monostearate, and fully stirring to obtain a pre-polymerization emulsion;
a2: preparing an initiating solution, specifically:
adding 0.05 part of initiator dicyclohexyl peroxydicarbonate and 0.4 part of sodium dodecyl benzene sulfonate into 5 parts of absolute ethyl alcohol by mass parts, and fully stirring to obtain a uniform initiating solution;
a3: preparing a polymerization solution, specifically:
weighing 100 parts of the pre-polymerization emulsion and 3 parts of the initiation solution respectively, then, dropwise adding 2/3 parts of the initiation solution (namely 2 parts of the initiation solution) into 100 parts of the pre-polymerization emulsion at 50 ℃ under stirring, stopping dropwise adding to obtain a mixed solution, heating the mixed solution to 75 ℃ at a heating rate of 3 ℃/min, then, dropwise adding 5 parts of polytetrahydrofuran diol, 0.09 part of chain extender triethylene glycol and the rest 1/3 part of the initiation solution (namely 1 part of the initiation solution) into the mixed solution at the same time at the temperature, heating to 85 ℃ after the dropwise adding of the three substances are completed, continuing to react for 55 minutes, and then, shearing at a high speed of 1000rpm until the emulsification is uniform to obtain a connecting base material, which is named as JL 1.
Preparation example 2: preparation of modified inorganic pigments
B1: grinding the inorganic pigment iron blue for many times until the particle size is less than or equal to 5 mu m, then adding the inorganic pigment iron blue into 10wt% of polyethylene glycol 200 aqueous solution (the mass ratio of the iron blue to the polyethylene glycol 200 in the polyethylene glycol 200 aqueous solution is 1.4:1), and fully stirring to obtain suspension; adding a sodium bicarbonate aqueous solution with the molar concentration of 0.8mol/L (the molar ratio of methacrylic acid to sodium bicarbonate is 1:0.12) into an aqueous solution with the methacrylic acid content of 10wt%, and fully stirring to obtain a mixed solution;
b2: adding ammonium persulfate into the mixed solution, stirring completely (the mass ratio of the ammonium persulfate to methacrylic acid in the mixed solution is 0.25:100), heating to 50 ℃, dropwise adding the suspension at the nitrogen atmosphere and the temperature (the mass ratio of the mixed solution to the suspension is 1:1.5), heating to 65 +/-2 ℃ after dropwise adding, carrying out heat preservation reaction for 35 minutes, filtering while hot after the reaction is finished, washing the filtrate with absolute ethyl alcohol, fully washing with deionized water until the eluate is neutral, and finally completely drying in vacuum to obtain the modified pigment which is named as YL 1.
Preparation examples 1.1 to 1.4: preparation of the jointing base
Preparation 1 was repeated to give preparations 1.1-1.4, except that the ramp rates in preparation 1, step A3 were changed from 3 deg.C/min to 1 deg.C/min, 5 deg.C/min, 2 deg.C/min and 4 deg.C/min, respectively, and the resulting linked matrices were designated DJL1, DJL2, DJL3 and DJL4 in that order.
Preparation examples 1.5 to 1.7: preparation of the jointing base
Preparation example 1 was repeated to give preparation examples 1.5-1.7, except that the nonionic surfactant in preparation example 1, step a1 was replaced with tetraethylene glycol monostearate with polyoxypropylene mannitol trioleate, tetraethylene glycol monooleate and polyoxypropylene stearate, respectively, and the resulting linked bases were designated DJL5, DJL6 and DJL7 in that order.
Preparation examples 2.1 to 2.2: preparation of modified inorganic pigments
Preparation example 2 was repeated to give preparation examples 2.1-2.2, except that the inorganic pigment iron blue in preparation example 2, step B1 was replaced with lead chrome yellow and iron oxide brown, respectively, and the resulting modified inorganic pigments were designated YL2 and YL3 in this order.
Stability testing of joint matrices
After preparation of JL1 from preparation example 1 and DJL1-DJL7 from preparation examples 1.1 to 1.7, they were immediately stored at room temperature in the absence of light and the stability after different storage times was examined and the results are shown in Table 1 below.
TABLE 1
Wherein in table 1 above: "+ + + +" indicates that the connecting base material has uniform shape, uniform color and no layering; "+ +" indicates that there was visually discernable unevenness in the color of the joining substrate under light (lower color was slightly darker and upper color was slightly lighter), but no delamination; "+" indicates delamination of the attached substrates.
It follows that the selection of the surfactant in step A1 is very important in the preparation of the joint matrix, with tetraethylene glycol monostearate having the best surface emulsifying properties, and that even very similar tetraethylene glycol monooleate suffers some degradation when replaced with other surfactants.
DJL5-DJL7 were not used in all of the following examples/comparative examples because of the reduced storage stability of DJL5-DJL 7.
Example 1: preparation of Water-based ink
S1: respectively weighing 30 parts of connecting base material JL1, 14 parts of modified inorganic pigment YL1, 1.5 parts of cosolvent triethylene glycol diglycidyl ether, 0.15 part of foam inhibitor 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol, 0.75 part of stabilizer 4, 4-butylene-bis (3-methyl-6-tert-butylphenol), 2.5 parts of emulsifier sodium hexadecylbenzene sulfonate, 1.5 parts of wetting agent (perfluoroalkyl polyoxypropylene polyoxyethylene ether with the structural formula of C)nF2n+1O(C3H6O)x(C2H4O)yR, wherein N is 8, x and y are respectively 6 and 20), 0.8 part of antioxidant (a mixture of isooctyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylate and N, N-bis (2, 4-diaminodiphenyl ether) imine in a mass ratio of 1: 1), 0.6 part of penetrant diisooctyl maleate sodium sulfonate, 1.5 parts of polyethylene wax and 35 parts of deionized water;
s2: adding the linking base, the modified inorganic pigment, the cosolvent, the foam inhibitor, the stabilizer, the wetting agent and the emulsifier (2 parts by mass) accounting for 80% of the total amount into the deionized water at 40 ℃, and shearing and dispersing at the speed of 1000rpm for 30 minutes to obtain a mixture;
s3: adding the antioxidant, the penetrating agent, the polyethylene wax and the rest emulsifier (0.5 part by mass) accounting for 20 percent of the total amount into the mixture, heating to 50 ℃, shearing and dispersing for 40 minutes at the speed of 1400rpm, sanding for many times until the fineness of the ink is less than or equal to 10 microns to obtain the water-based ink which is named as Y1.
Example 2: preparation of Water-based ink
S1: respectively weighing 25 parts of connecting base material JL1, 16 parts of modified inorganic pigment YL2, 1 part of cosolvent triethylene glycol diglycidyl ether, 0.2 part of foam inhibitor 2,5,8, 11-tetramethyl-6-dodecenyl-5, 8-diol, 0.5 part of stabilizer 4, 4-butylene-bis (3-methyl-6-tert-butylphenol), 3 parts of emulsifier lauric acid monoglyceride and 1 part of wetting agent (perfluoroalkyl polyoxypropylene polyoxyethylene ether with the structural formula of C)nF2n+1O(C3H6O)x(C2H4O)yR, wherein N is 8, x and y are respectively 10 and 14), 1 part of antioxidant (a mixture of isooctyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylate and N, N-bis (2, 4-diaminodiphenyl ether) imine in a mass ratio of 1: 1), 0.4 part of penetrant diisooctyl maleate sodium sulfonate, 2 parts of polyethylene wax and 30 parts of deionized water;
s2: adding the binder, the modified inorganic pigment, the cosolvent, the foam inhibitor, the stabilizer, the wetting agent and the emulsifier (i.e., 2.4 parts by mass) in an amount of 80% of the total amount to the deionized water at 40 ℃, and shearing and dispersing at 1400rpm for 20 minutes to obtain a mixture;
s3: adding the antioxidant, the penetrating agent, the polyethylene wax and the rest emulsifier (0.6 part by mass) accounting for 20 percent of the total amount into the mixture, heating to 50 ℃, shearing and dispersing for 50 minutes at the speed of 1000rpm, sanding for many times until the fineness of the ink is less than or equal to 10 microns to obtain the water-based ink, which is named as Y2.
Example 3: preparation of Water-based ink
S1: respectively weighing 35 parts of connecting base material JL1, 12 parts of modified inorganic pigment YL3, 2 parts of cosolvent triethylene glycol diglycidyl ether, 0.1 part of foam inhibitor 2,5,8, 11-tetramethyl-6-dodec-5, 8-diol, 1 part of stabilizer 4, 4-butylene-bis (3-methyl-6-tert-butylphenol), 2 parts of emulsifier sucrose ester triglycerol monostearate and 2 parts of wetting agent (perfluoroalkyl polyoxypropylene polyoxyethylene ether with the structural formula of C)nF2n+1O(C3H6O)x(C2H4O)yR, wherein N is 8, x and y are respectively 8 and 17), 0.6 part of antioxidant (a mixture of isooctyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylate and N, N-bis (2, 4-diaminodiphenyl ether) imine in a mass ratio of 1: 1), 0.8 part of penetrant diisooctyl maleate sodium sulfonate, 1 part of polyethylene wax and 40 parts of deionized water;
s2: adding the linking base, the modified inorganic pigment, the cosolvent, the foam inhibitor, the stabilizer, the wetting agent, and the emulsifier (i.e., 1.6 parts by mass) in an amount of 80% of the total amount to the deionized water at 40 ℃, and shearing and dispersing at 1200rpm for 25 minutes to obtain a mixture;
s3: adding the antioxidant, the penetrating agent, the polyethylene wax and the rest emulsifier (0.4 part by mass) accounting for 20 percent of the total amount into the mixture, heating to 50 ℃, shearing and dispersing for 45 minutes at the speed of 1200rpm, sanding for many times until the fineness of the ink is less than or equal to 10 microns to obtain the water-based ink which is named as Y3.
Comparative examples 1 to 4: preparation of Water-based ink
The examples 1-3 were repeated except that the joining base JL1 in examples 1-3 was replaced by DJL1-DJL4, respectively, and the joining bases used, the correspondence and the resulting water-based ink nomenclature are as follows in Table 2.
TABLE 2
Comparative examples 5 to 7: preparation of Water-based ink
Examples 1-3 were repeated except that triethylene glycol diglycidyl ether, which is the cosolvent in examples 1-3, was replaced with the other cosolvents listed below, and the cosolvents used, the correspondence, and the resulting aqueous ink are given the following nomenclature in Table 3.
TABLE 3
Comparative examples 8 to 11: preparation of Water-based ink
Examples 1-3 were repeated except that the suds suppressors 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol of examples 1-3 were replaced with other suds suppressors as follows, respectively, and the suds suppressors used, the corresponding relationships, and the resulting aqueous inks were named as shown in Table 4 below.
TABLE 4
Comparative examples 12 to 13: preparation of Water-based ink
The procedure of example 1-2 was repeated except that the stabilizer 4, 4-butylidene-bis (3-methyl-6-tert-butylphenol) in example 1-2 was replaced with tris (nonylphenyl) phosphite and 2, 6-di-tert-butyl-p-cresol, respectively, and the resulting aqueous inks were designated as D12 and D13 in this order.
Comparative examples 14 to 15: preparation of Water-based ink
Examples 1-2 were repeated except that n in the wetting agents of examples 1-2 was replaced with 6 and 10, respectively, and the resulting aqueous inks were designated as D14 and D15 in this order.
Testing of Water-based inks
1. Storage stability test
After the aqueous inks of the above-mentioned examples and comparative examples were prepared, they were immediately stored at room temperature in the dark, and the stability after various storage times was examined, the results of which are shown in Table 5 below.
TABLE 5
Wherein in table 5 above: "+ + + +" indicates that the water-based ink has uniform shape, uniform color, no layering and no floccule; "+ +" indicates that there was visually discernable unevenness in the color of the aqueous ink under light (lower color was slightly darker and upper color was slightly lighter), but no delamination, no floc; "+" indicates that there was some floc, but no delamination, in addition to visually discernable unevenness (lower color slightly darker and upper color slightly lighter) in the aqueous ink under light; and "-" indicates that not only a little floc but also foam is present on the surface, but no delamination occurs.
It can be seen from this that: 1. the rate of temperature increase in step a3 is very important in the preparation of the linking base, the best stability is obtained at 3 ℃/min, while the greater the deviation from 3 ℃/min, the poorer the storage stability, which should be the best polymerization at this temperature; 2. triethylene glycol diglycidyl ether has the best effect (even if the similar ethylene glycol diglycidyl ether is obviously reduced) on the cosolvent, which is to say that the substance has the optimal cosolvent effect on the final connecting base material, the modified inorganic pigment and the like, so that the optimal dissolved state can be effectively maintained; 3. for the antifoaming agent, 2,5,8, 11-tetramethyl-6-dodecene-5, 8-diol has the best antifoaming effect, which should be because the existence of its dihydroxy group and multi-branched methyl group can generate the best hydrophilic-lipophilic arrangement on the ink surface, thereby inhibiting the formation and generation of foam.
2. Test of Peel Strength
The test standard of the peel strength is GB/T2790, specifically, each water-based ink is printed on a polyvinyl chloride film by a gravure printer, after the printing is finished, the water-based ink is dried completely, a hot press is used for hot pressing for 8 seconds at 150 ℃, and then the peel strength test is carried out according to the GB/T2790 standard, and the results are shown in Table 6 below.
TABLE 6
The peel strength was an average value for each water-based ink in the same group.
It can be seen from this that: 1. the water-based ink Y1-Y3 has very excellent organic film peeling strength, so that the water-based ink can be applied to printing of organic films such as food packages; 2. it was again demonstrated that the rate of temperature rise in step a3 is very important in the preparation of the joint matrix, achieving the best print strength at 3 ℃/min, while the greater the deviation at 3 ℃/min, the poorer the peel strength, again due to the difference in the polymerization strength of the polymeric joint matrix at different rates of temperature rise; 3. when the value of n in the wetting agent is changed, the peeling strength is also reduced, which proves that the printing adhesion strength with the organic film is reduced due to the reduction of the wetting property at that time.
3. Gloss measurement
The aqueous inks of the examples and comparative examples were gravure printed with the same parameters, the printed substrate was a high density polyethylene film, the printing was completed and dried thoroughly, and after 60 days at 50 ℃ under continuous illumination (intensity of 4500lux), gloss measurements were made on each printed ink layer using a gloss meter (menenda MG268), the results of which are given in table 7 below, and the same values were averaged for each group.
TABLE 7
Wherein, for the same group, the gloss is the average value of each aqueous ink, wherein the "+" of D12-D13 indicates that the fading phenomenon of the printing ink layer occurs.
It can be seen from this that: 1. the water-based ink of the invention has excellent gloss performance, which proves that the printing performance is excellent; 2. it is again demonstrated that the rate of temperature rise in step a3 is very important in the preparation of the joining base, the best gloss performance is achieved at 3 ℃/min, while the greater the deviation from 3 ℃/min, the poorer the gloss, which is also the difference in surface roughness and hence in gloss performance due to the difference in polymerization strength of the polymeric joining base at different rates of temperature rise; 3. the difference in suds suppressors also significantly affects the final gloss level, which is why minute surface bubbles are generated; 4. of the stabilizers, 4, 4-butylidene-bis (3-methyl-6-tert-butylphenol) had the best stabilizing effect, and the other stabilizers caused the occurrence of discoloration.
Investigation of emulsifier addition at different stages in the preparation method
In order to investigate the influence of different adding times of the emulsifier on the performance of the final water-based ink in the preparation method of the invention, the following comparative tests are carried out.
Comparative examples 16 to 18: the operations of examples 1 to 3 were repeated except that all the emulsifiers were added at once in step S2 (i.e., not added in step S3), and the resulting aqueous inks were named D16, D17 and D18 in this order.
Comparative examples 19 to 21: the operations of examples 1 to 3 were repeated except that all the emulsifiers were added at once in step S3 (i.e., not added in step S2), and the resulting aqueous inks were named D19, D20 and D21 in this order.
The storage stability test was carried out in the same manner as in the "1, storage stability test" described above, and the results are shown in Table 8 below (results of Y1-Y3, D1-D15 are shown together).
TABLE 8
Wherein in table 8 above: the meanings of "+ + + + +", "+" and "-" are the same as the corresponding meanings in Table 5, and "-" in this table indicates that significant demixing occurs, which demonstrates that significant instability can occur after long storage when the emulsifier is added all at once, which should be due to the fact that the best emulsifying properties cannot be achieved due to the different hydrophilic and lipophilic tendencies of the individual components after one addition. However, when the addition is carried out stepwise, the hydrophilic-lipophilic tendencies of the respective components are optimally balanced in steps S2 and S3, respectively, resulting in the best long-term storage stability of the final aqueous ink.
Examination of the unmodified inorganic pigments
To examine the effect of the inorganic pigment being unmodified in the aqueous ink of the present invention, the following comparative test was conducted.
Examples 1-3 were repeated except that equal masses of the corresponding inorganic pigments were used in place of the modified inorganic pigments (i.e., the inorganic pigments were used without modification), and the resulting aqueous inks were designated D22, D23, and D24 in that order.
The results of the adhesion strength test were obtained in the same manner as in the above "test for peel strength 2" and are shown in Table 9 below (the results of Y1-Y3 and D1-D15 are shown together).
TABLE 9
The peel strength was an average value for each water-based ink in the same group.
It can be seen that when the inorganic pigment is not modified, the peel strength is reduced to some extent, because when the inorganic pigment is not modified, the adhesion of the inorganic pigment to an oleophilic printing substrate is reduced, so that the peel strength is reduced, and a good printing state cannot be maintained for a long time, which proves that the modification can remarkably improve the bonding state of the inorganic pigment and a hydrophobic substrate, and is particularly suitable for printing or printing treatment of hydrophobic substrates such as films, plastics and the like.
As described above, the invention provides the water-based ink, the preparation method and the application thereof, and the water-based ink has good properties through the preferable selection and mutual cooperation of a plurality of components and the special treatment of certain unique components, thereby having good application prospect and industrial production potential in the printing field.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should also be understood that various alterations, modifications and/or variations can be made to the present invention by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the protective scope defined by the claims of the present application.
Claims (10)
1. The water-based ink comprises a connecting base material, a modified inorganic pigment, a cosolvent, a foam inhibitor, a stabilizer, an emulsifier, a wetting agent, an antioxidant, a penetrating agent, polyethylene wax and deionized water;
the connecting base material is prepared according to the following steps:
a1: preparing a pre-polymerization emulsion, specifically:
at room temperature, adding a mixture of 1 part of glycidyl methacrylate and 1.5 parts of vinyl propionate into 10 parts of deionized water according to parts by mass, adding 0.1 part of nonionic surfactant, and fully stirring to obtain a pre-polymerization emulsion;
a2: preparing an initiating solution, specifically:
adding 0.04-0.06 part of initiator and 0.4 part of sodium dodecyl benzene sulfonate into 5 parts of absolute ethyl alcohol by mass part, and fully stirring to obtain a uniform initiating solution;
a3: preparing a polymerization solution, specifically:
weighing 100 parts of the pre-polymerization emulsion and 3 parts of the initiation solution respectively according to the mass parts, then, under stirring, firstly, dropwise adding 2/3 parts of the initiation solution into 100 parts of the pre-polymerization emulsion at 50 ℃, then stopping dropwise adding to obtain a mixed solution, heating the mixed solution to 75 ℃ at the heating rate of 3 ℃/min, then, dropwise adding 5 parts of polytetrahydrofuran diol, 0.06-0.12 part of chain extender and the rest 1/3 of the initiation solution into the mixed solution at the same time at the temperature, heating to 85 ℃ after all three substances are dropwise added, continuing to react for 50-60 min, and then, shearing at the high speed of 1000rpm until emulsification is uniform, thus obtaining the connecting base material;
in the step a1, the nonionic surfactant is selected from any one of polyoxypropylene mannitol trioleate, tetraethylene glycol monostearate, tetraethylene glycol monooleate or polyoxypropylene stearate;
the modified inorganic pigment is prepared by the following steps:
b1: grinding the inorganic pigment for many times until the granularity is less than or equal to 5 mu m, then adding the inorganic pigment into 10wt% of polyethylene glycol 200 aqueous solution, and fully stirring to obtain suspension; adding a sodium bicarbonate aqueous solution with the molar concentration of 0.8mol/L into an aqueous solution with the methacrylic acid content of 10wt%, and fully stirring to obtain a mixed solution;
b2: adding ammonium persulfate into the mixed solution, stirring completely, heating to 50 ℃, dropwise adding the ammonium persulfate into the suspension at the nitrogen atmosphere and the nitrogen atmosphere, heating to 65 +/-2 ℃ after dropwise adding, keeping the temperature for reaction for 30-40 minutes, filtering while hot after the reaction is finished, washing the filtrate with absolute ethyl alcohol, fully washing with deionized water until the eluate is neutral, and finally completely drying in vacuum to obtain the modified inorganic pigment;
the cosolvent is triethylene glycol diglycidyl ether;
the foam inhibitor is 2,5,8, 11-tetramethyl-6-dodecene-5, 8-diol;
the stabilizer is 4, 4-butylene-bis (3-methyl-6-tert-butylphenol).
2. The aqueous ink of claim 1, wherein: the water-based ink comprises the following components in parts by mass:
connecting base material 25-35
Modified inorganic pigments 12 to 16
Cosolvent 1-2
0.1-0.2 of foam inhibitor
0.5-1 part of stabilizer
Emulsifier 2-3
Wetting agent 1-2
0.6-1 part of antioxidant
Penetrating agent 0.4-0.8
Polyethylene wax 1-2
30-40 parts of deionized water.
3. The aqueous ink of claim 2, wherein: the water-based ink comprises the following components in parts by mass:
connecting base 30
Modified inorganic pigment 14
Cosolvent 1.5
Suds suppressor 0.15
Stabilizer 0.75
Emulsifier 2.5
Wetting agent 1.5
0.8% of antioxidant
Penetrant 0.6
Polyethylene wax 1.5
Deionized water 35.
4. The aqueous ink according to any one of claims 1 to 3, wherein: in the step a1, the nonionic surfactant is tetraethylene glycol monostearate.
5. The aqueous ink according to any one of claims 1 to 3, wherein: the emulsifier is any one of sodium hexadecylbenzene sulfonate, lauric monoglyceride, sucrose ester triglycerol monostearate and sorbitan tristearate.
6. The aqueous ink according to any one of claims 1 to 3, wherein: the wetting agent is perfluoroalkyl polyoxypropylene polyoxyethylene ether, and the structural formula of the wetting agent is CnF2n +1O (C3H6O) x (C2H4O) yR, wherein n is an integer between 6 and 10, and x and y are integers between 6 and 10 and 14 and 20 respectively.
7. The aqueous ink according to any one of claims 1 to 3, wherein: the antioxidant is a mixture of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl acrylate and N, N-bis (2, 4-diaminodiphenyl ether) imine in a mass ratio of 1:1.
8. The aqueous ink according to any one of claims 1 to 3, wherein: the penetrating agent is diisooctyl maleate sodium sulfonate.
9. A method for preparing an aqueous ink according to any one of claims 1 to 8, said method comprising the steps of:
s1: weighing each component according to the respective mass content;
s2: adding a connecting base material, a modified inorganic pigment, a cosolvent, a foam inhibitor, a stabilizer, a wetting agent and an emulsifier accounting for 80 percent of the total amount into deionized water at 40 ℃, and shearing and dispersing at the speed of 1000-1400rpm for 20-30 minutes to obtain a mixture;
s3: adding an antioxidant, a penetrating agent, polyethylene wax and the rest emulsifier accounting for 20 percent of the total amount into the mixture, heating to 50 ℃, continuing to shear and disperse for 40-50 minutes at the speed of 1000-1400rpm, and sanding for many times until the fineness of the ink is less than or equal to 10 microns to obtain the water-based ink.
10. Use of the aqueous ink according to any one of claims 1 to 8 in the field of printing.
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| CN105176187A (en) * | 2015-09-02 | 2015-12-23 | 王景泉 | Silver adhesive/gold powder bright adhesive waterproof cloth screen printing aqueous ink and preparation method thereof |
| CN107384013A (en) * | 2017-09-11 | 2017-11-24 | 杭州海维特化工科技有限公司 | A kind of PVC furniture film intaglio printing water-based ink and preparation method thereof |
| CN108587318A (en) * | 2018-08-01 | 2018-09-28 | 湖南七纬科技有限公司 | A kind of advertising and printing water-based ink and preparation method thereof |
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| CN104559465A (en) * | 2013-10-24 | 2015-04-29 | 中国科学院化学研究所 | Environment-friendly aqueous printing ink and preparation method thereof |
| CN105176187A (en) * | 2015-09-02 | 2015-12-23 | 王景泉 | Silver adhesive/gold powder bright adhesive waterproof cloth screen printing aqueous ink and preparation method thereof |
| CN107384013A (en) * | 2017-09-11 | 2017-11-24 | 杭州海维特化工科技有限公司 | A kind of PVC furniture film intaglio printing water-based ink and preparation method thereof |
| CN108587318A (en) * | 2018-08-01 | 2018-09-28 | 湖南七纬科技有限公司 | A kind of advertising and printing water-based ink and preparation method thereof |
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