CN102086324B - Water-based ink used for nonabsorbent substrates and preparation method thereof - Google Patents
Water-based ink used for nonabsorbent substrates and preparation method thereof Download PDFInfo
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Abstract
The invention relates to water-based ink used for nonabsorbent substrates and a preparation method thereof. The water-based ink comprises the following components by weight percent: 40-60% of colorant, 20-50% of emulsion, 5-15% of water and water-soluble solvent and 1-15% of ink additive, wherein the colorant comprises the following components by weight percent: 5-10% of water, 8-20% of water-soluble solvent, 20-40% of resin dispersion, 0-5% of dispersant and 5-40% of pigment. The preparation method comprises the following steps: 1) preparing colorant, 2) adding emulsion to stir; 3) adding the mixture of water and water-soluble solvent to adjust the viscosity; 4) adding ink additive to finally adjust the performances; and 5) filtering and packaging. The invention has the following beneficial effects: through the integration and optimization of the formula, defoaming agent is not used at all, thus the water-based ink formula causing formation shrinkage cavity defect is not adopted and the water-based ink which does not uses defoaming agent, has fewer foams and good wetting effect and has excellent printing performance and physical performance on various nonabsorbent substrates, can be prepared.
Description
Technical field
The present invention relates to water color ink for gentle version and intaglio plate and preparation method thereof, especially a kind of nonabsorbable ground water color ink and preparation method thereof that is common to.
Background technology
As the important directions that solves security against fire, reduces petroleum resource consumption, reduces the workshop air environmental pollution and improve the food product pack hygienic requirements, for printing ink and printing industry, a generally acknowledged common recognition is development and uses water color ink.In this field, there has been numerous investigators to carry out ground-breaking work, yet, most research and use all is confined to absorbent substrates (as various coatings and non-overlay paper) field, application on the nonabsorbable ground is very few, and subject matter is that wetting, dry and solution adhesion problem of water color ink is all more difficult.in addition, this paper has also noticed and has related to more in recent years document or the patent that the nonabsorbable ground is used, be CN101029194A (plastic-film water gravure printing printing ink) as publication number, publication number is CN1290728 (water color ink and the manufacture method thereof that are used for plastic film relief printing), publication number is CN101054490A (water multipurpose plastic compound with surface printing series ink and preparation method thereof), publication number is CN1702126A (a kind of aqueous ink used for plastic), publication number is CN101570657 (a kind of paper, plastics water-based ink and preparation method) etc., yet adopt the printing ink of the making of formula shown in above patent in actual application, along with ground difference or substrate surface change of state, the variation of printing condition etc., be easy to occur bubbling, the problem of shrinkage cavity or moistening badness, be difficult in other words obtain high-quality printed matter, although this also just industry carried out a large amount of effort on water color ink, but the reason that does not almost have in the practical application to all kinds of nonabsorbable grounds.
by systematic research, we find that above-mentioned patent has certain law on China ink processed, for example all used the acid of small molecular weight co-polypropylene (usually also to have vinylbenzene except vinylformic acid in formula, maleic anhydride or other one-tenth copolymer composition that grades, in this article all referred to as co-polypropylene acid) resinoid ammonia solution, and macromolecule co-polypropylene yogurt liquid, we know, the co-polypropylene acid resin can present a kind of nature of soap structure after ammonification, bubble than being easier to, emulsion is due to a large amount of uses of emulsifying agent, be more prone to bubble, on the other hand, because the surface tension of water is large, wetting ability to various nonabsorbable grounds is very poor, sometimes also must add the surface tension of specific decreasing by surfactant system in order to overcome this problem, this has just more aggravated the whipability of system, can say, easily bubbling is the greatest problem of water color ink, problem is, above-mentioned patent all simultaneously use defoamer carry out foam control, the kind of defoamer comprises mineral oil, vegetables oil, water drain silica, stearate soap, organo-siloxane and other organic defoamers, and defoamer itself is to utilize to carry out froth breaking with the inconsistent principle of system, defoaming effect is better for defoamer consistency poorer (as organo-siloxane), but meanwhile, this inconsistent characteristic is easy to cause the shrinkage cavity of filming on ground, the tendency of this shrinkage cavity can be along with the kind of defoamer, consumption, the difference of ground printing ink through the time aging and change, in other words, so long as used defoamer, under certain conditions, film and to show certain shrinkage cavity tendency.Regrettably, do not provide the way that addresses this problem in above-mentioned patent, or say and do not recognize the adverse consequences of using defoamer to cause.
Summary of the invention
Purpose of the present invention is just in order to overcome the deficiency of above-mentioned technology, and a kind of nonabsorbable ground water color ink and preparation method thereof that is common to is provided, it all can be used on as various nonabsorbable grounds commonly used such as aluminized paper, aluminium foil (or aluminum foil composite paper), films (as PP, PE, PET, PVC etc.) smoothly.
The present invention solves the technical scheme that its technical problem adopts: this nonabsorbable ground water color ink that is common to, and the formulation weight ratio is: mill base 40～60%, emulsion 20～50%, water and water-soluble solvent 5～15%, ink addition agent 1～15%; The formula of mill base is: water 5～10%, water-soluble solvent 8～20%, dispersion resin liquid 20～40%, dispersion agent 0～5%, pigment 5～40%.Do not use defoamer in formula, being characterized as of defoamer: a kind of or compound in mineral oil, vegetables oil, water drain silica, stearate soap, organo-siloxane and other organic defoamers.
The making method that is common to nonabsorbable ground water color ink of the present invention, step is as follows:
The making of A, mill base;
B, add emulsion to mix;
C, the mixture that adds entry and water-soluble solvent carry out viscosity to be adjusted;
D, add ink addition agent to carry out final property regulation;
E, filtration and packing;
As preferably, the dispersion resin liquid that uses in paste formula, exist at whipped state, add successively entry 20～50%, water-soluble solvent 10～30, caustic solubility co-polypropylene acid resin 20～40%, basic cpd 3～10 in stirring tank, insulation dissolving under 50～80 degrees centigrade.
As preferably, used caustic solubility co-polypropylene acid resin in dispersion resin liquid, number-average molecular weight 5000～40000, acid value 50～300; Having used basic cpd in dispersion resin liquid, is one or more in organic basic cpd or mineral-type basic cpd; What use basic cpd in dispersion resin liquid is to make the formula neutralization ratio reach 80～200%.
As preferably, having used dispersion agent in mill base is the polymeric dispersant of high molecular, and the pigment of use is organic or inorganic pigment.
As preferably, in step B: emulsion is used the emulsion of soap-free polymerization mode polymerization, and the soap-free emulsion number-average molecular weight is 50000～250000; Acid number is between 50～150; Solid content is 30～50%; The emulsion add-on accounts for the formula gross weight than 20～50%, need to add under the state of stirring at low speed, and the linear velocity of stirring rake is the highest can not surpass 10m/s.
As preferably, in step C: water with add again after water-soluble solvent must mix, with the problem that prevents that system from breakdown of emulsion occurring, separating out, the mixed weight ratio is water: water-soluble solvent=3: 7～between 9: 1.Water-soluble solvent can be to carry out with water any organic solvent of mixing, contain one or more in the polyfunctional group solvent of alcohol, ether group as lower molecular weight ketone, alcohols, ethers, part nitrogenous compound solvent such as N-Methyl pyrrolidone, part, most suitable as low carbon chain alcohols (containing C6 and following) such as ethanol, propyl alcohol, butanols and as polyfunctional group alcohol ether solvents such as glycol ether, propylene glycols, the very few effect that do not reach of consumption, too much consumption will make the system loss of stability.
As preferably, in step D: comprise wax, wetting agent, pH adjusting agent, thickening material, solidifying agent, wax is one or more in its polyethylene wax, oxidized polyethlene wax, tetrafluoroethylene wax, paraffin, amide waxe, and wetting agent is polyether modified silicane, fluorochemical surfactant or acetylenic diols tensio-active agent; The pH adjusting agent is one or more in organic basic cpd or mineral-type basic cpd; Solidifying agent is one or more in burnett's solution, oxazoline class, titanic acid ester, nitrogen the third ingot, carbonization diamines material.
As preferably, printing ink adopts closed sand milling dispersing technology to carry out processing and manufacturing, first uses sand mill mill base to be carried out the grinding distribution work of pigment, adds resin, the ink addition agent composition of rear interpolation to complete ink formulations after to be ground completing synthetic again.
At first to use a kind of emulsion of low whipability, with the whipability of the hierarchy of control a comparatively gentle degree.can learn that by the composition in analysis system the small-molecular emulsifier that contains in emulsion is the foaming source of system maximum, the kind of emulsifying agent, different its whipabilitys of content are had nothing in common with each other, adopt a kind of method can distinguish fast the whipability of emulsion according to characteristic of the present invention herein: with (water: mixed solvent ethanol=3: 1) carries out 100% dilution to sample, getting the 50ml diluent packs into airtight in the 250ml vial, carrying out taking out standing 10 minutes after the standard concussion in the concussion instrument fast, observe the foam height in sample bottle: (foam height 10ml is 1 grade to carry out classification take 10ml as gradient by the height of foam, 20ml is 2 grades, 30ml is 3 grades, 40ml is 4 grades, 50ml and above be 5 grades), 1 grade is judged to be low whipability emulsion with 2 grades, preferred 1 grade.This method also is applicable to the discriminating of other composition whipabilitys in follow-up formula.The application direction of considering this paper is mainly nonabsorbable ground field, and small-molecular emulsifier also can cause detrimentally affect to water tolerance and the sticking power of system simultaneously, therefore further preferably considers the emulsion of using the soap-free polymerization mode to make.Do not contain or only contain the small-molecular emulsifier of trace in this emulsion, but emulsion copolymerization on molecule segment has water-soluble monomer, also auxiliary reaction emulsifier or the macromolecule emulsifying agent of using carries out (certainly) emulsification usually, the whipability of this emulsion is generally lower.Except common co-polypropylene acids type, or the soap-free polymerization emulsion has also comprised the stable polyaminoester emulsion acrylic/polyurethane hybridisation emulsion of employing self-emulsifying mode, be not particularly limited in this article, and a common ground between emulsion is: the emulsifying agent that does not contain or only contain trace in emulsion.Aspect emulsion polymerisation process, can find a large amount of open source literatures at present, the last word of the productions such as manufacturers both domestic and external such as BASF, ROHM AND HAAS, Nuplex Resins can both reach practical level in printing ink is used, thereby will directly select commerical prod in this article but not own making.Another advantage of this emulsion is higher than ordinary emulsion to the degree of holding of alcohol, ethers water-soluble solvent, and this is conducive to the application of following the 2nd narrating content.
Add water-soluble solvent to carry out system surface tension adjustment and foam control.The printing ink that uses above-mentioned emulsion to make is lubricated and wetting owing to lacking the conduct of small molecules tensio-active agent, system presents the phenomenons such as bad, the unfairness of filming of flowing, although system has obtained certain control on whipability, yet the elimination of foam is still very slow.We test various (except using defoamer) method, the effect of improving is all very limited, yet but we are when adding water-soluble solvent and being increased to certain dosage in system, wonderful discovery, the whipability of printing ink has obtained very significantly suppressing, the elimination of produced simultaneously foam is very rapid, and the quality of filming also is greatly improved.This effect is to have utilized the characteristic of water-soluble solvent oleophylic, low surface tension (when water-soluble solvent adds fashionable, the surface tension of system solvent (water) phase reduces, lipophilicity increases, the orientation of amphiphilic substance reduces and then the stability of foam reduces, thereby reaches the effect that presses down bubble).
The effect that the present invention is useful is: by the integrated optimization of formula, thereby realize fully without defoamer avoid the filming water-soluble printing ink formula of shrinkage cavity defect, produce and a kind ofly need not use defoamer fully and bubble seldom, wetting effect is good, all has very good printing performance and the water color ink of physicals simultaneously on various nonabsorbable grounds.
Embodiment
The invention will be further described below in conjunction with embodiment:
Composition and engineering of the present invention divides following steps:
The making of A, mill base (Ji Mo);
B, add emulsion to mix
C, the mixture that adds entry and water-soluble solvent carry out viscosity to be adjusted
D, add ink addition agent to carry out final property regulation
E, filtration and packing.
Mill base (Ji Mo) for the A part heavily occupies 40～60% in the ink formulations gross weight, and what the most generally use is to adopt the closed sand mill to carry out the technique of pigment grind, and the composition in mill base (Ji Mo) and formula are as follows:
For the pigment dispersing resin liquid in formula, due to the foam of the commodity of selling on market in order to produce in the production control process, usually the defoamer that wherein all contains, therefore in the present invention, dispersion resin liquid adopts oneself making, all do not contain defoamer but replace in formula and add water-soluble solvent, set forth above principle, formula and technique are as follows:
The molten type co-polypropylene of above-mentioned alkali acid resin, we have directly selected market commodity on sale, can enumerate but having of being not limited only to: JOHNCRYL 67 (BASF), JOHNCRYL678 (BASF), NeoCryl B817 (DSM) etc., the standard of selecting is: number-average molecular weight 5000～40000, acid value 50～300.
Above-mentioned basic cpd Main Function is that the acidic-group in the co-polypropylene acid resin is neutralized, and then solvability and the pigment-dispersed of raising resin, can enumerate but be not limited only to: the organic basic cpds such as methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, ternary, Monoethanolamine MEA BASF, diethanolamine, trolamine, the perhaps alkali-metal oxyhydroxide such as potassium, sodium; The alkali-metal carbonate such as potassium, sodium; The carbonate of the alkaline-earth metal such as calcium, barium; Ammonium hydroxide etc.The consumption of basic cpd is according to the setting of the system neutralization ratio calculating that feeds intake:
Neutralization ratio (%)=((basic cpd quality (g) * 56 * 1000)/(resin acid value * basic cpd equivalent * resin quality (g)) * 100
Neutralization ratio is set in 80～200% in this formula, is preferably 80～120%.
The main points of above-mentioned formula are to use water-soluble solvent to replace defoamer to control foam.
Mill base (Ji Mo) for the A part is made, also can adopt the method for pigment color chips (grinding or kneader kneading technique dispersed color with two roller machines) dissolving to carry out, but integral formulation composition and top described approaching, principle, addition that the use of water solvent and basic cpd use are all undertaken by top described principle, therefore no longer are described in detail in this article.
For the B part, namely the emulsion part, account for the formula gross weight than 20～50%, need to add under the state of stirring at low speed, and the linear velocity of stirring rake is the highest can not surpass 10m/s.
For the C part, need to add the adjusting that entry and water-soluble solvent carry out system viscosity, it must be emphasized that here water and water-soluble solvent add after must mixing again, with the problem that prevents that system from breakdown of emulsion occurring, separating out, mixing the suggestion of (weight) ratio exists: (water: between water-soluble solvent)=(3: 7)～(9: 1), total amount is in 5～15% weight ratios.
for the D part, general total amount is no more than 15%, mainly that use wax slurry or wax emulsion (are generally polyethylene waxs, oxidized polyethlene wax, tetrafluoroethylene wax, paraffin, one or more in amide waxe), wetting agent (polyether modified silicane, fluorochemical surfactant or acetylenic diols tensio-active agent), PH adjusting agent (aforesaid basic cpd), thickening material (modified-cellulose or polyurethanes associative thickener), Deng, sometimes in order further to promote the performance of printing ink, also can add some solidifying agent, as burnett's solution, the oxazoline class, titanic acid ester, nitrogen the third ingot, one or more in the materials such as carbonization diamines.
Above A, B, C, D part all add complete after, use mechanical stirring to mix printing ink and can enter the inspection after construction stage, can enter E after qualified is packing stage.
Implementation example: the formula rate described in embodiment is weight ratio:
Embodiment one: the making example E-1 of dispersion resin liquid E, after mixing, 32 parts of 33 parts of weighing deionized waters, propylene glycol monomethyl ether start stirring, (BASF produces acrylic resin to drop into successively JOHNCRYL 67 under whipped state, acid number 213: 10 parts of molecular weight Mw12500) 25 parts, ammoniacal liquor (28% concentration), the rising temperature also remains on 60 degrees centigrade, insulation makes resin liquid thoroughly dissolve more than 2 hours, regulate and measure pH value between 8～10, filter discharging, obtain dispersion resin liquid E-1
Embodiment two: the making example E-2 of dispersion resin liquid E, after mixing, 15 parts of 45 parts of weighing deionized waters, Virahol start stirring, (BASF produces acrylic resin to drop into successively JOHNCRYL 678 under whipped state, acid number 215: molecular weight Mw8500 :) 10 parts of 30 parts, 2-amino-2-methyl-1-propanol, the rising temperature also remains on 60 degrees centigrade, insulation makes resin liquid thoroughly dissolve more than 2 hours, regulate and measure pH value between 8～10, filter discharging, obtain dispersion resin liquid E-2
embodiment three: printing ink to manufacture example Y-1: 10 parts of weighing deionized waters, 5 parts of ethanol, 1 part of pigment dispersing agent (SOLOSPERSE27000, Lubrizol company produce), 15 parts of PY14 yellow pigments (DIC company produce), 40 parts of E-1 dispersion resin liquid use stirrer to mix more than 30 minutes until mix in stirring tank, send in sand mill (BUHLER K-60) and carry out pigment grind, stop grinding after being ground to pigment maximum particle diameter≤15 micron, start stirring, add YJ-HD8708-YJ soap-free emulsion (solid content 40% in weighing under whipped state, molecular weight 80,000, acid number 100, 70 degrees centigrade of second-order transition temperatures, 42 degrees centigrade of Shanghai spark bases of minimum film-forming temperature provide) stirred 20 minutes after 20 parts, continue to stir, weighing adds the mixture (5 parts of 3 parts/ethanol of deionized water) of deionized water and ethanol, adds at last 1 part, polyethylene wax slurry (Mai Kemen company product, 40% solid content), rear filtration stirs, be packaged to be the printing ink finished product, resulting printing ink can be observed foaming seldom, and at aluminized paper, aluminium foil, aluminum foil composite paper, film (PP, PE, PET, good sticking power is all arranged PVC), and wettability is good simultaneously.
embodiment four: printing ink to manufacture example Y-1: 5 parts of weighing deionized waters, 10 parts of n-propyl alcohols, titanium dioxide is (domestic, rutile-type) 28 parts, 20 parts of E-2 dispersion resin liquid use stirrer to mix more than 30 minutes until mix in stirring tank, send in sand mill (BUHLER K-60) and carry out pigment grind, stop grinding after being ground to pigment maximum particle diameter≤15 micron, start stirring, add YJ-HD8740 soap-free emulsion (solid content 45% in weighing under whipped state, molecular weight 150,000, acid number 50, 20 degrees centigrade of second-order transition temperatures, 3 degrees centigrade of Shanghai spark bases of minimum film-forming temperature provide) stirred 20 minutes after 30 parts, continue to stir, weighing adds the mixture (2 parts of 3.5 parts/n-propyl alcohols of deionized water) of deionized water and ethanol, adds at last 1 part, polyethylene wax slurry (Mai Kemen company product, 40% solid content), 0.2 part of ground wetting agent (Surfynol 104E, aerochemistry produces), rear filtration stirs after 0.3 part of silicon dioxide powder (Degussa product), be packaged to be the printing ink finished product.Resulting printing ink can be observed foaming seldom, and on aluminized paper, aluminium foil, aluminum foil composite paper, film (PP, PE, PET, PVC), good sticking power is arranged all, and wettability is good simultaneously.
The making Comparative Examples E-3 of Comparative Examples one, dispersion resin liquid E, 59.8 parts of weighing deionizations, drop into successively 0.2 part of defoamer (BYK024) under whipped state, (BASF produces acrylic resin to JOHNCRYL 678, acid number 215: molecular weight Mw8500 :) 10 parts of 30 parts, 2-amino-2-methyl-1-propanol, the rising temperature also remains on 60 degrees centigrade, and insulation makes resin liquid thoroughly dissolve more than 2 hours, regulate and measure pH value between 8～10, filter discharging, obtain dispersion resin liquid E-3
Comparative Examples two, printing ink to manufacture example Y-3: weighing deionized water 14.9, 0.1 part of defoamer (BYK024), titanium dioxide is (domestic, rutile-type) 28 parts, 20 parts of E-3 dispersion resin liquid use stirrer to mix more than 30 minutes until mix in stirring tank, send in sand mill (BUHLER K-60) and carry out pigment grind, stop grinding after being ground to pigment maximum particle diameter≤15 micron, start stirring, add Johncryl 74J emulsion (solid content 45% in weighing under whipped state, molecular weight 〉=2,000,000,000, acid number 51, 22 degrees centigrade of second-order transition temperatures, 5 degrees centigrade of minimum film-forming temperatures, BASF provides) stirred 20 minutes after 30 parts, continue to stir, weighing adds the mixture (2 parts of 3.5 parts/n-propyl alcohols of deionized water) of deionized water and ethanol, adds at last 1 part, polyethylene wax slurry (Mai Kemen company product, 40% solid content), 0.2 part of ground wetting agent (Surfynol 104E, aerochemistry produces), rear filtration stirs after 0.3 part of silicon dioxide powder (Degussa product), be packaged to be the printing ink finished product.It is less that resulting printing ink can be observed foaming, and on aluminized paper, aluminium foil, aluminum foil composite paper, film (PP, PE, PET, PVC), good sticking power is arranged all.
Use deionized water to be diluted to identical viscosities to printing ink Y-1, Y-2, Y-3, use Weng Kaier K101 coating instrument to be coated with on different grounds, and in standard light source first to the X-ray examination X paint film defect:
Symbol implication in table: zero expression is filmed good, and △ represents visible minor defects, * represent visible open defect
Can find out from above-mentioned test, adopt the printing ink that the present invention makes to obtain perfect coating when coating.
Aforementioned is the preferred embodiment of the present invention, yet, those skilled in the art should understand that as long as without prejudice to the spirit and scope of the present invention, can be to the invention process numerous variations and modification.
Claims (6)
1. making method that is common to nonabsorbable ground water color ink, it is characterized in that: step is as follows:
The making of A, mill base; The mill base add-on accounts for 40～60% of formula gross weight ratio, the formula of mill base is: water 5～10%, water-soluble solvent 8～20%, dispersion resin liquid 20～40%, dispersion agent 0～5%, pigment 5～40%, the dispersion resin liquid that uses in paste formula, under whipped state, add successively entry 20～50%, water-soluble solvent 10～30, caustic solubility co-polypropylene acid resin 20～40%, basic cpd 3～10 in stirring tank, insulation dissolving under 50～80 degrees centigrade;
B, add emulsion to mix; Emulsion is used the emulsion of soap-free polymerization mode polymerization, and the soap-free emulsion number-average molecular weight is 50000～250000; Acid number is between 50～150; Solid content is 30～50%; The emulsion add-on accounts for 20～50% of formula gross weight ratio, need to add under the state of stirring at low speed, and the linear velocity of stirring rake is the highest can not surpass 10m/s;
C, the mixture that adds entry and water-soluble solvent carry out viscosity to be adjusted, and water and water-soluble solvent add-on account for 5～15% of formula gross weight ratio;
D, add ink addition agent to carry out final property regulation, the ink addition agent add-on accounts for 1～15% of formula gross weight ratio;
E, filtration and packing.
2. the making method that is common to nonabsorbable ground water color ink according to claim 1, is characterized in that: used caustic solubility co-polypropylene acid resin in dispersion resin liquid, number-average molecular weight 5000～40000, acid value 50～300; Having used basic cpd in dispersion resin liquid, is one or more in organic basic cpd or mineral-type basic cpd; What use basic cpd in dispersion resin liquid is to make the formula neutralization ratio reach 80～200%.
3. the making method that is common to nonabsorbable ground water color ink according to claim 1, it is characterized in that: the dispersion agent that uses in mill base is the polymeric dispersant of high molecular, the pigment of use is organic or inorganic pigment.
4. the making method that is common to nonabsorbable ground water color ink according to claim 1 is characterized in that: in step C: water with add again after water-soluble solvent must mix, the mixed weight ratio is between water: water-soluble solvent=3:7～9:1.
5. the making method that is common to nonabsorbable ground water color ink according to claim 1, it is characterized in that: in step D: ink addition agent comprises wax, wetting agent, pH adjusting agent, thickening material, solidifying agent, wax is one or more in its polyethylene wax, oxidized polyethlene wax, tetrafluoroethylene wax, paraffin, amide waxe, and wetting agent is polyether modified silicane, fluorochemical surfactant or acetylenic diols tensio-active agent; The pH adjusting agent is one or more in organic basic cpd or mineral-type basic cpd; Solidifying agent is one or more in burnett's solution, oxazoline class, titanic acid ester, nitrogen the third ingot, carbonization diamines material.
6. the making method that is common to nonabsorbable ground water color ink according to claim 1, it is characterized in that: printing ink adopts closed sand milling dispersing technology to carry out processing and manufacturing, first use sand mill mill base to be carried out the grinding distribution work of pigment, add again resin, the ink addition agent composition of rear interpolation to complete ink formulations after to be ground completing synthetic.
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| CN101717596A (en) * | 2009-12-08 | 2010-06-02 | 杭华油墨化学有限公司 | Water-based ink for package printing of high-adhesion film and manufacturing method thereof |
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| CN102086324A (en) | 2011-06-08 |
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