CN100497489C - Method for preparing nano pigment water-borne dispersion - Google Patents
Method for preparing nano pigment water-borne dispersion Download PDFInfo
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- CN100497489C CN100497489C CNB2006101186713A CN200610118671A CN100497489C CN 100497489 C CN100497489 C CN 100497489C CN B2006101186713 A CNB2006101186713 A CN B2006101186713A CN 200610118671 A CN200610118671 A CN 200610118671A CN 100497489 C CN100497489 C CN 100497489C
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Abstract
This invention discloses a kind of aqueous dispersion of the nano pigment and its preparation method. The said method is fixing the hydrophobic colorant fully dissolved in polymer monomers into the nano microballoons of the cross linking polymers at the molecule-separate and colorant-aggregative-phase state by using the modified polyreaction in fine latex to obtain the seeds of prepolymerization, then constructing a modified and protective cross linking encloser of the polymer by the enveloping polyreaction, and finally making the nano pigment grains stably disperse in the water medium dissolved with the surface activating agent at a low concentration. The invented aqueous dispersion of the nano pigment is suitable for aqueous ink-jet color marking ink in high performance and color-screened distemper pieces used for making liquid crystal display devices. It can also be applied in pigmentation of the coatings, pigment materials of the high-end cosmetics and so on.
Description
Technical field
The present invention relates to a kind of preparation method's of colorant, particularly a kind of nano-coloring material aqueous dispersions preparation method.This nano-coloring material aqueous dispersions is applicable to high performance hydrate colour ink-jet printing ink and the colored filter mill base that is applied to make liquid-crystal display, in addition, also can be applicable to pigment coloration, the cosmetics of super quality with colorant etc.
Background technology
On broad sense, mixture and dispersion system thereof less than pigment particles, dyestuff or the pigment of 100nm on the yardstick all can be referred to as nano-coloring material (nanocolorants).And nano-coloring material feature of the present invention is: they significantly are different from the nano dye (nanopigments) that obtains by physical methods such as mechanical mill, micronizing or vapor phase processs.On system structure, this class nano-coloring material is a class nano-complex that gets up by non covalent bond mode mortise as the hydrophobic dyestuff of color component and suitable nanometer polymer particle matrix, and its performance objective is the weather resistance that not only can keep the excellent colour characteristics of the dyestuff that uses but also can realize excellence.At present, the preparation method of nano-coloring material aqueous dispersions has following several:
1, the Arno J. of German BASF AG
Deng people (Presented at the High PerformancePigments Conference, 1998, Barcelona, Spain and 61st Annual Technical Conference (ANTEC2003), Nashville, TN, US, volume 2 in 2003) at first utilizes miniemulsion (miniemulsion) polymerization process to prepare the new colorant of a class and be referred to as nano-coloring material, be applied to coloring plastic, makeup and functional additive such as white dyes, UV absorption agent etc., but the photostabilization of its product, high-temperature stability and stability in storage are not appeared in the newspapers.
2, the people such as Barashkov of U.S. Radiant Color company (Presented at Int.Conf.on DigitalPrinting Technologies 2001, Fort Lauderdale, US) adopt dyestuff encapsulation technology (Dye-PackagingTechnology, DPT) prepared a kind of fluorescence nano colorant that is used for the aqueous jet printing, this technology adopts traditional emulsion polymerization that water miscible fluorescence dye is sealed less than the polymer particle of 140nm with median size, and the colorant of acquisition has good water-fast, photostabilization.But there are shortcomings such as dosage of surfactant is big, the particle diameter controllability is relatively poor, dyestuff content is low in this method.
3, Ri Ben people such as M.Takasu have reported (Colloid Polym.Sci., 2003 282 volumes and 2005 283 volumes) do not adding linking agent, do not adding in addition under the condition of co-stabilizer (hydrophober), select the high hydrophobic azo class oil-soluble dyes that solvability is high in vinylbenzene for use and add hindered amine as light stabilizer, make the higher color nanometer latex (colored nanolatex) of dyestuff content by the mini-emulsion polymerization reaction; Be reflected at the emulsion particle surface introducing polyureas shell of colorization then by interfacial polycondensation.Their method mainly concentrates on to study and how to improve dyestuff retain stability and light stability in emulsion particle, and lacks the research for its particle morphology structure, size-grade distribution and color property.
Summary of the invention
The objective of the invention is to guarantee the colour characteristics of colorant excellence and realize good fast light/time property, in conjunction with stability and stability in storage etc., a kind of preparation method of nano-coloring material aqueous dispersions is provided.In addition, other purposes of the present invention are to provide a kind of high performance red, yellow, green or blue nano-coloring material aqueous dispersions.
The concrete preparation method of a kind of nano-coloring material aqueous dispersions of the present invention is as follows, below all represents with mass parts:
(1) mini-emulsion polymerization of modification reaction:
0.4～1 part of emulsifier sodium lauryl sulfate and 0.06～1.6 part of pH value conditioning agent sodium bicarbonate are dissolved in the beaker that 100 parts of deionized waters are housed, as water; 12～30 parts of vinylbenzene of stopper, 1～5 part of methyl methacrylate and 0.5～4 part of linking agent Vinylstyrene are removed in underpressure distillation in advance, be added in another beaker, add 0.7～5 part of hydrophobic dyestuff, 0.1～0.3 part of droplet nucleation promotor and 0.06～0.2 part of response type hindered amine as light stabilizer again, the dissolving back is as oil phase fully; Water is poured in the oil phase, be that 1000～1800 rev/mins of mechanical stirring are after 15～30 minutes at room temperature with rotating speed, place the thin emulsification of ultrasonic homogenizer then under ice-water bath, its ultrasonic power is 400～500 watts, and thin emulsification obtained miniemulsion after 10～20 minutes; The miniemulsion for preparing all packed into be connected in the four-hole boiling flask of stirring, thermometer, prolong and nitrogen tube, heat up after feeding nitrogen deoxygenation in 20～40 minutes earlier, rise to after 55～60 ℃ and inject the aqueous solution that 0.05～0.3 part of Potassium Persulphate is dissolved in 3～8 parts of deionized waters with syringe, the beginning initiated polymerization, remain on 62～68 ℃ and reacted 1～2 hour down, obtain prepolymer seeds;
Hydrophobic dyestuff wherein is anthraquinone type orchil, anthraquinone type yellow dyes, anthraquinone type green colouring material or anthraquinone type blue dyes; Droplet nucleation promotor is that molecular weight is 20,000～70,000 polystyrene particulate; But the response type hindered amine as light stabilizer is a hindered amine as light stabilizer for the piperidines of copolyreaction;
(2) the involucrum polyreaction of prepolymer seeds:
Take by weighing 1～4 part of hydroxyethyl methylacrylate, methacrylic acid or methyl methacrylate, 0.1～0.5 part of Ethylene glycol dimethacrylate or 1, the 4-butylene glycol diacrylate, add and be equipped with in the beaker of 10 parts of deionized waters, add 0.1～0.4 part of emulsifying agent polyoxyethylene nonylphenol ether and 0.01～0.02 part of Potassium Persulphate again, under ice-water bath with rotating speed be 500～1000 rev/mins stir 15～25 minutes after, obtain the involucrum polymerized emulsion; Drip the involucrum polymerized emulsion in prepolymer seeds, the time of dropping is 0.5～1 hour, guarantees to feed in raw material with starvation, dropwises the back and continues reaction end reaction after 2～3 hours down at 62～68 ℃; In polymerization process, sampling detects monomer polymerization reactions by gas chromatograph and transforms situation, exists up to definite monomer-free; Promptly obtain nano-coloring material aqueous dispersions after removing by filter impurity at last.
The nano-coloring material aqueous dispersions that the present invention obtains comprises the median size of nano-coloring material particle and the stability in storage investigation of particle size distribution measuring, Zeta potential mensuration, measurement of surface tension, rotation viscosity measurement and aqueous dispersion through a series of sign and test; Also designed analysis test method combining that stability is estimated and fast light/marquis's property of product is compared test voluntarily to dyestuff in the nano-coloring material particle and polymeric matrix.
The preparation method's of a kind of nano-coloring material aqueous dispersions of the present invention characteristics are as follows:
1), at first, on the basis that with nonpolar vinylbenzene is main polymerization single polymerization monomer, introduces an amount of polar monomer methyl methacrylate and have important effect.Because it is incomplete that the interface of miniemulsion drop is that tensio-active agent covers, in order further to reduce the interfacial energy of oil/water, the interface region that these more hydrophilic polar monomers will trend towards concentrating on drop high hydrophobic dyestuff simultaneously then is pushed to the inside of drop.Correspondingly, the hydrophobic dyestuff of skin that the polar polymer major part is positioned the nanometer polymer particle after polyreaction proceeds to the to a certain degree inside of most of imbedded particle then; In addition, the appropriately crosslinked of polymkeric substance also is indispensable.Hydrophobic dyestuff existence in the nano-coloring material particle of the present invention is: all be dissolved with the dyestuff of higher concentration in the monomer droplet, when polyreaction was carried out, more a spot of dye molecule was owing to the sucking action that is subjected to the cross-linked macromolecular chain is attached on the macromolecular chain; More dyestuff then forms the dyestuff gathering mutually and then be embedded in the inside of a macromole ball of string because dyestuff in the polymerization process and polymerization single polymerization monomer as solvent are separated.The crosslinked of polymkeric substance can significantly reduce its free volume and cause polymkeric substance outside more closely, and significant inhibition and barrier effect are played in motion/migration that dye molecule and dyestuff are assembled mutually.In view of above 2 points, the present invention has realized hydrophobic dyestuff and the mortise of nanometer polymer particle matrix under the non covalent bond condition.
2), the involucrum polyreaction is the cross-linked polymer shell of the prepolymer seeds particle structure protectiveness of mini-emulsion polymerization reaction acquisition; strengthened dyestuff set stability in the nanometer polymer microballoon; intercept the infringement of outside oxygen, reagent etc., thereby further strengthened thermostability and fast light/marquis's property of product.In addition, monomers such as hydrophilic methyl methacrylate, especially water miscible hydroxyethyl methylacrylate, methacrylic acid are at the crosslinking polymerization on surface, thereby the surface modification that has realized product obtains excellent stability in storage, and has created condition for the further application of product.
3) but, the hindered amine as light stabilizer of an amount of copolyreaction of dissolving in the miniemulsion drop, make after the polyreaction nano-coloring material particle structurally covalent bonding the photostabilizer component is arranged, guarantee the light stability of dyestuff and polymeric matrix.
Characterize and the result of analytical test shows, nano-coloring material aqueous dispersions of the present invention has the water dispersion character of excellence: median size is less than 100nm, and polydispersity index is less than 0.08 high granularity uniformity; Greater than the high surface tension of 53mN/m, less than the low rotation viscosity of 1.5cP, less than-high the Zeta potential of 52mV and outstanding stability in storage; The dye sheet that uses in the nano-coloring material of the present invention reveals good and the stability that combines polymeric matrix, and the dyestuff that uses than correspondence has the fast light/marquis's property that improves greatly.This nano-coloring material aqueous dispersions is applicable to high performance hydrate colour ink-jet printing ink and the colored filter mill base that is applied to make liquid-crystal display; In addition, also can be applicable to pigment coloration, the cosmetics of super quality with colorant etc.
Description of drawings
To the evaluation method that combine stability of dyestuff in the nano-coloring material particle with polymeric matrix, Fig. 1 is the nano-coloring material aqueous dispersions that obtains of embodiment and the ultraviolet-visible absorption spectroscopy figure of corresponding dyestuff according to the present invention.
Embodiment
The testing tool that the present invention adopts is as follows: ultraviolet-visual spectrometer (Lambda 20, Perkin Elmer); Photon correlation spectrometer (Zetasizer Nano S, Malvern Instruments) is measured the median size (Z of nano-coloring material
Ave) and size distribution (polydispersity index PDI); Zetasizer Nano ZS instrument (Malvern Instruments) is measured Zeta potential; The full-automatic surface tension instrument of BZY-1 type (Shanghai Hengping Instrument ﹠ Meter Plant) is measured surface tension; NDJ-1 type rotational viscosimeter (the Shanghai flat scientific instrument of perseverance company) is measured the rotation viscosity.
The analysis test method that the present invention adopts is as follows:
1) the present invention is to the evaluation method in conjunction with stability of dyestuff in the nano-coloring material particle with polymeric matrix: the dyestuff of meticulous toner that obtains after the nano-coloring material aqueous dispersions spraying drying and corresponding use is doped in polystyrene (weight-average molecular weight Mw=280 respectively, make color foil 000g/mol), place the ethanol under the comparatively high temps to obtain to contain the solution that moves the dyestuff that comes out, then it is carried out the ultraviolet-visible absorption spectroscopy comparative analysis, wherein comparative sample is the thin slice that is made by corresponding dyestuff.This colorful polystyrene thin slice is produced as follows: 0.2 part of 1.8 parts of meticulous toners and corresponding dyestuff is added respectively in 50 parts the polystyrene, utilize Haake rheology torque meter (model Rheocorel 90) to make colorant and polystyrene, utilize vulcanizing press under 190 ℃, mixture to be pressed into the thick thin slice of 1cm then 175 ℃ of following full and uniform mixing.Clip 1.0g colorful polystyrene thin slice places the sealing in the bottle of 15 milliliters of dehydrated alcohols is housed, and leaves standstill in 70 ℃ thermostat container 60 hours, extracts the solution that obtains then and carries out the UV, visible light absorption analysis.When dye strength in the ethanol was very low, according to the Beer law, the height of UV, visible light optical density can reflect the dye strength height that migration is come out from polystyrene dielectric in direct ratio ground.So, can obtain the information of combination of dyes stability in the nano-coloring material particle by the ultraviolet-visible absorption spectroscopy that contrasts corresponding dyestuff;
2) the stability in storage investigation method of nano-coloring material aqueous dispersions: sample was statically placed in room temperature following 90 days, observed flocculation, throw out etc. whether occur, and nothing flocculation and throw out then are evaluated as outstanding after 90 days;
3) the present invention to nano-coloring material fast light/comparative evaluation's method of marquis's property: at first nano-coloring material and corresponding dyestuff are made separately colour film, the colour film of being made by dyestuff is sample as a comparison.0.01 part of dyestuff is dissolved in 5 parts of dehydrated alcohols then in the polyvinyl alcohol water solution of the 15wt.% of thorough mixing to 20 part, obtains to be coated with film system; The nano-coloring material aqueous dispersions of respective color directly joins in the polyvinyl alcohol water solution of 15wt.%, thorough mixing, and acquisition has the film system that is coated with of identical dyestuff content.Utilize the spin coating instrument to be spun on the hard paper being coated with film system, dry back obtains the colour film separately of thickness basically identical.Colour film is placed apart from xenon lamp 6 ± 1 centimeters Continuous irradiation 120 hours, and wherein xenon lamp illumination is 30,000 luxes, keep the colour film heating temperature 60～80 ℃ and relative humidity 30～50%.Then sample is passed through
The desk-top colourimeter of XE (HunterLab Co.) is measured the aberration (Δ E) behind the colour film pre-irradiation, aberration more little then fast light/Hou Xingyue is good.
The anthraquinone type orchil that the following examples are used is C.I. solvent red 168, C.I. solvent red 146 or C.I. solvent red 138, the anthraquinone type yellow dyes is C.I. solvent yellow 16 3 or C.I. solvent yellow 189, the anthraquinone type green colouring material is C.I. solvent green 28 or C.I. solvent green 3, and the anthraquinone type blue dyes is C.I. solvent blue 3R, C.I. solvent blue 97 or C.I. solvent blue 45; But the piperidines of copolyreaction is a hindered amine as light stabilizer is GW-628 (Shanxi Province chemical research institute), ADK Stab LA-82 or 87 (Japanese Asahi Electro-Chemical Co. Ltd) or HA-R100 (atropic chemistry); The emulsifying agent polyoxyethylene nonylphenol ether is OP-10.
Embodiment 1:
(1) mini-emulsion polymerization of modification reaction:
0.65g sodium lauryl sulphate and 0.1g part pH value conditioning agent sodium bicarbonate are dissolved in the beaker that the 100g deionized water is housed, as water; Underpressure distillation is in advance removed 16g vinylbenzene, 2g methyl methacrylate and the 1.9g linking agent Vinylstyrene of stopper, be added in another beaker, add 1.3g C.I. solvent red 168,0.16g droplet nucleation promotor and 0.08g response type hindered amine as light stabilizer GW-628 again, the dissolving back is as oil phase fully; Water is poured in the oil phase, is 1200 rev/mins of mechanical stirring after 20 minutes with rotating speed at room temperature, places the thin emulsification of ultrasonic homogenizer then under ice-water bath, and its ultrasonic power is 450 watts, and thin emulsification obtained miniemulsion after 15 minutes; The miniemulsion for preparing is packed in the 250ml four-hole boiling flask that is connected to stirring, thermometer, prolong and nitrogen tube, heat up after feeding nitrogen deoxygenation in 25 minutes earlier, rise to after 60 ℃ and inject the aqueous solution that the 0.16g Potassium Persulphate is dissolved in the 5g deionized water with syringe, the beginning initiated polymerization, remain under 65 ℃ of constant temperature and reacted 1.5 hours, obtain prepolymer seeds;
(2) the involucrum polyreaction of prepolymer seeds:
Take by weighing 2.5g part hydroxyethyl methylacrylate, 0.6g Ethylene glycol dimethacrylate, add and be equipped with in the beaker of 16g deionized water, add 0.2g emulsifier op-10 and 0.015g Potassium Persulphate again, under the ice-water bath with rotating speed be 800 rev/mins stir 20 minutes after, obtain the involucrum polymerized emulsion, in 50 milliliters the constant pressure funnel of packing into, be connected on the four-hole boiling flask; Drip the involucrum polymerized emulsion in prepolymer seeds, the time of dropping is controlled to be 0.5 hour, dropwises the back and finish reaction after 65 ℃ continuation is reacted 3 hours down; In polymerization process, sampling detects monomer polymerization reactions by gas chromatograph and transforms situation, exists up to definite monomer-free.Promptly obtain the red nano coloring material aqueous dispersions after removing a small amount of large granular impurity with the common filter paper decompress filter of multilayer at last.
The final red nano coloring material aqueous dispersions 136.5g that obtains, wherein solid content is 18.1wt.%; The dyestuff that shows good aqueous dispersion character (seeing Table 1), comparison correspondence has the fast light/marquis's property (seeing Table 2) that promotes greatly; The comparison of optical density from the ultraviolet-visible spectrogram of Fig. 1 (see among Fig. 1 in the curve 1 and Fig. 1 curve 4) can learn that dyestuff has the good stability that combines in the nano-coloring material particle.
Embodiment 2:
According to embodiment 1, oil phase is a 2g C.I. solvent yellow 16 3 in the reaction of change mini-emulsion polymerization, and all the other prescriptions are identical with technology.
The final Yellow nanometer coloring material aqueous dispersions 137g that obtains, wherein solid content is 18.5wt.%; The dyestuff that shows good aqueous dispersion character (seeing Table 1), comparison correspondence has the fast light/marquis's property (seeing Table 2) that promotes greatly; The comparison of optical density from the ultraviolet-visible spectrogram of Fig. 1 (see among Fig. 1 in the curve 2 and Fig. 1 curve 5) can learn that dyestuff has the good stability that combines in the nano-coloring material particle.
Embodiment 3:
According to embodiment 1, oil phase is a 0.8g C.I. solvent green 28 in the reaction of change mini-emulsion polymerization, and all the other prescriptions are identical with technology.
The final Preen nono coloring material aqueous dispersions 135.7g that obtains, wherein solid content is 17.8wt.%; The dyestuff that shows good aqueous dispersion character (seeing Table 1), comparison correspondence has the fast light/marquis's property (seeing Table 2) that promotes greatly.Embodiment 4:
According to embodiment 1, oil phase is 2.5g C.I. solvent blue 3R in the reaction of change mini-emulsion polymerization, and all the other prescriptions are identical with technology.
The blue nano-coloring material aqueous dispersions 137.5g of final acquisition, wherein solid content is 18.8wt.%; The dyestuff that shows good aqueous dispersion character (seeing Table 1), comparison correspondence has the fast light/marquis's property (seeing Table 2) that promotes greatly.The comparison of optical density from the ultraviolet-visible spectrogram of Fig. 1 (see among Fig. 1 in the curve 3 and Fig. 1 curve 6) can learn that dyestuff has the good stability that combines in the nano-coloring material particle.
Comparative Examples 1,2,3 and 4 be respectively according to the present invention to nano-coloring material fast light/colour film of redness, yellow, green and the blue dyes of the preparation of comparative evaluation's method of marquis's property.
The nano-coloring material aqueous dispersions character that four embodiment of table 1. obtain
The nano-coloring material aqueous dispersions that table 2. embodiment obtains compares with fast light/marquis's property of the colour film of corresponding dyestuff preparation.
Claims (1)
1. the preparation method of a nano-coloring material aqueous dispersions is characterized in that its preparation method is as follows, below all represents with mass parts:
(1) mini-emulsion polymerization of modification reaction:
0.4～1 part of emulsifier sodium lauryl sulfate and 0.06～1.6 part of pH value conditioning agent sodium bicarbonate are dissolved in the beaker that 100 parts of deionized waters are housed, as water; 12～30 parts of vinylbenzene of stopper, 1～5 part of methyl methacrylate and 0.5～4 part of linking agent Vinylstyrene are removed in underpressure distillation in advance, be added in another beaker, add 0.7～5 part of hydrophobic dyestuff, 0.1～0.3 part of droplet nucleation promotor and 0.06～0.2 part of response type hindered amine as light stabilizer again, the dissolving back is as oil phase fully; Water is poured in the oil phase, be that 1000～1800 rev/mins of mechanical stirring are after 15～30 minutes at room temperature with rotating speed, place the thin emulsification of ultrasonic homogenizer then under ice-water bath, its ultrasonic power is 400～500 watts, and thin emulsification obtained miniemulsion after 10～20 minutes; The miniemulsion for preparing all packed into be connected in the four-hole boiling flask of stirring, thermometer, prolong and nitrogen tube, heat up after feeding nitrogen deoxygenation in 20～40 minutes earlier, rise to after 55～60 ℃ and inject the aqueous solution that 0.05～0.3 part of Potassium Persulphate is dissolved in 3～8 parts of deionized waters with syringe, the beginning initiated polymerization, remain on 62～68 ℃ and reacted 1～2 hour down, obtain prepolymer seeds;
Hydrophobic dyestuff wherein is anthraquinone type orchil, anthraquinone type yellow dyes, anthraquinone type green colouring material or anthraquinone type blue dyes; Droplet nucleation promotor is that molecular weight is 20,000～70,000 polystyrene particulate; But the response type hindered amine as light stabilizer is a hindered amine as light stabilizer for the piperidines of copolyreaction;
(2) the involucrum polyreaction of prepolymer seeds:
Take by weighing 1～4 part of hydroxyethyl methylacrylate, methacrylic acid or methyl methacrylate, 0.1～0.5 part of Ethylene glycol dimethacrylate or 1, the 4-butylene glycol diacrylate, add and be equipped with in the beaker of 10 parts of deionized waters, add 0.1～0.4 part of emulsifying agent polyoxyethylene nonylphenol ether and 0.01～0.02 part of Potassium Persulphate again, under ice-water bath with rotating speed be 500～1000 rev/mins stir 15～25 minutes after, obtain the involucrum polymerized emulsion; Drip the involucrum polymerized emulsion in prepolymer seeds, the time of dropping is 0.5～1 hour, guarantees to feed in raw material with starvation, dropwises the back and continues reaction end reaction after 2～3 hours down at 62～68 ℃; In polymerization process, sampling detects monomer polymerization reactions by gas chromatograph and transforms situation, exists up to definite monomer-free; Promptly obtain nano-coloring material aqueous dispersions after removing by filter impurity at last.
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| CN101601984B (en) * | 2009-07-07 | 2011-06-22 | 河北工业大学 | Nonylphenol polyoxyethylene ether dimeric surfactant using piperazine as connecting group |
| CN104693840A (en) * | 2013-12-06 | 2015-06-10 | 上海华明高技术（集团）有限公司 | Environment-friendly nanometer pigment water-borne dispersion and preparation method thereof |
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| CN101486845A (en) * | 2008-01-14 | 2009-07-22 | 深圳市海川实业股份有限公司 | Method for preparing nano colouring matter aqueous dispersions |
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| CN101601984B (en) * | 2009-07-07 | 2011-06-22 | 河北工业大学 | Nonylphenol polyoxyethylene ether dimeric surfactant using piperazine as connecting group |
| CN104693840A (en) * | 2013-12-06 | 2015-06-10 | 上海华明高技术（集团）有限公司 | Environment-friendly nanometer pigment water-borne dispersion and preparation method thereof |
| CN104693840B (en) * | 2013-12-06 | 2016-10-05 | 上海华明高技术（集团）有限公司 | Environment-friendly type nano coloring material aqueous dispersions and preparation method thereof |
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