CN101955708A - Method for preparing nano microcapsule water-based color paste - Google Patents
Method for preparing nano microcapsule water-based color paste Download PDFInfo
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Abstract
The invention relates to a method for preparing nano microcapsule water-based color paste. The method comprises the following steps of: fixing water-repellent dye which is fully dissolved in a polymeric monomer in cross-linked polymer nanoparticles in the molecular dispersion state and the dye aggregation phase state by a mini-emulsion polymerization reaction so as to obtain a pigment capsule core of a micro-capsule; and constructing a polymer shell, namely, a capsule wall with self-film forming property and self-crosslinking property at normal temperature on the surface of the capsule core by cladding polymerization reaction technology so as to obtain the nano micro-capsule color paste stably dispersed in a water medium. The nano micro-capsule water-based color paste of the invention can keep excellent color property of the used dye and realize high durability (light resistance/weather resistance and storage stability), self-film forming property and self-crosslinking property at normal temperature; and the color paste is suitable for coloring with high-performance textile inkjet printing pigment ink, colored inkjet printing ink, water-based ink and coatings and is applied to color paste for a colored optical filter for manufacturing a liquid crystal display.
Description
Technical field
The present invention relates to a kind of preparation method of nano aqueous mill base, particularly a kind of preparation method of capsule of nano type aqueous color paste.This capsule of nano type mill base is applicable to high performance textile inkjet printing coating ink, color inkjet printing ink and the colored filter mill base that is applied to make liquid-crystal display, in addition, also can be applicable to water color ink and pigment coloration etc.Belong to the Chemicals preparing technical field.
Background technology
At present, the preparation method with aqueous color paste of capsule of nano type structure has following several:
The people such as Barashkov of U.S. Radiant Color company (Presented at Int.Conf.on Digital Printing Technologies 2001, Fort Lauderdale, US) adopt dyestuff encapsulation technology (Dye-Packaging Technology) to prepare 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.
The people such as M.Takasu of Japan 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, 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.
CN1978552 discloses a kind of preparation method of nano-coloring material aqueous dispersions.Utilize the reaction of improved mini-emulsion polymerization be dissolved in fully in the polymerization single polymerization monomer hydrophobic dye with molecular dispersion state and dyestuff gathering mutually state be fixed in the cross-linked polymer Nano microsphere, obtain prepolymer seeds; Then utilize the involucrum polymerization technique to make up cross-linked polymer shell modification, protectiveness on the seed particles surface.The colorant water dispersion of this method preparation has the structure of similar capsule of nano, but it does not possess self film-formed and self-crosslinking required when using.
CN1817981 discloses a kind of used for textiles nanometer painting ink-jetting printing oil ink and preparation method thereof.Printing ink is made up of pigment microcapsule, self-crosslinking polymer fine latex, deionized water, water-miscible organic solvent, sanitas, wetting Agent for Printing Inks, tensio-active agent and pH regulator agent.Its preparation method is: earlier colo(u)rant dispersion is become nanometer particle, make the water-soluble polymer precipitating on the pigment particles surface with non-solvent then, be formed on the pigment capsule of nano of stable dispersion in the water, pigment microcapsule and other components are mixed by a certain percentage, promptly get ink-jet printing ink.CN101020795 discloses a kind of preparation method of ink for ink jet printing of leather, and its method is in fact similar with the CN1817981 publication.As seen, above-mentioned two preparation methods still do not break away from traditional pigment physics and disperse means.
On broad sense, all can be referred to as nano color paste by the water-based or the oil dispersion system that obtain less than the mixture of pigment particles, dyestuff or the pigment of 100nm on the yardstick.
Summary of the invention
Purpose of the present invention, be for a kind of preparation method of capsule of nano type aqueous color paste being provided, adopting the aqueous color paste of this method preparation not only can keep the excellent colour characteristics of used dyestuff but also can realize excellent weather resistance (fast light/time property, stability in storage), self film-formed and ambient self-crosslinking.
Purpose of the present invention reaches by following measure:
A kind of preparation method of capsule of nano type aqueous color paste is characterized in that may further comprise the steps, and wherein related material is represented with mass parts:
1) mini-emulsion polymerization prepared in reaction capsule of nano capsule-core
0.4～1 part of emulsifying agent and 0.06～0.3 part of pH value conditioning agent sodium bicarbonate are dissolved in the beaker that 100 parts of deionized waters are housed, as water; Removing 12～30 parts of vinylbenzene of stopper, 1～5 part of methyl methacrylate and 0.5～3 part of linking agent with the washing of 5% caustic-soda aqueous solution 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 20～30 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 10～20 minutes earlier, inject the aqueous solution that 0.05～0.3 part of Potassium Persulphate is dissolved in 3～8 parts of deionized waters with syringe when rising to 55～60 ℃, the beginning initiated polymerization, remain on 62～66 ℃ of following stirring reactions 1～2 hour, and obtained the microcapsule capsule-core;
2) the involucrum polyreaction prepares cyst wall
Take by weighing 12～50 parts of butyl acrylates, 6～30 parts of methyl methacrylates, 1～5 part of hydroxyethyl methylacrylate or methacrylic acid and 3～10 parts of diacetone-acryloamide(DAA)s, add and be equipped with in the beaker of 20～50 parts of deionized waters, add 0.2～0.6 part of emulsifier sodium lauryl sulfate, 0.4～1.2 part of emulsifying agent peregal 0-15 and 0.1～0.8 part of Potassium Persulphate or ammonium persulphate again, under the normal temperature with rotating speed be 300～900 rev/mins stir 30～60 minutes after, obtain involucrum polymerization pre-emulsion; Drip the involucrum polymerized emulsion in the microcapsule capsule-core, keep the capsule-core temperature, the dropping time is 2.5～3 hours, guarantees with starvation reinforcedly, is warming up to 68～73 ℃ after dropwising and continues stirring reaction down and finishes after 1～2 hour to react; Be cooled to and add ammoniacal liquor after the room temperature to regulate the pH value be 6～8, add 10～50 part 10% the adipic dihydrazide aqueous solution then, stir; Promptly obtain capsule of nano type aqueous color paste after removing small amount of impurities with 0.22 μ m millipore filtration at last.
First purpose of the present invention can also reach by taking following measure:
One embodiment of the present invention are: this preparation method carries out according to the following steps, below all represents with mass parts:
1) mini-emulsion polymerization prepared in reaction capsule of nano capsule-core
0.65 part of emulsifying agent and 0.1 part of pH value conditioning agent sodium bicarbonate are dissolved in the beaker that 100 parts of deionized waters are housed, as water; Removing 16 parts of vinylbenzene of stopper, 2 parts of methyl methacrylates and 1.5 parts of linking agents with the washing of 5% white liquor in advance, be added in another beaker, add 1.3 parts of hydrophobic dyestuffs, 0.16 part of droplet nucleation promotor and 0.08 part of response type photostabilizer 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 15 minutes earlier, inject the aqueous solution that 0.16 part of Potassium Persulphate is dissolved in 5 parts of deionized waters with syringe when rising to 60 ℃, the beginning initiated polymerization, remain under 65 ℃ of constant temperature and reacted 1.5 hours, obtain the microcapsule capsule-core;
2) the involucrum polyreaction prepares cyst wall
Take by weighing 16 parts of butyl acrylates, 7 parts of methyl methacrylates, 3 parts of hydroxyethyl methylacrylates and 5 parts of diacetone-acryloamide(DAA)s, add and be equipped with in the beaker of 25 parts of deionized waters, add 0.3 part of emulsifier sodium lauryl sulfate, 0.6 part of emulsifying agent peregal 0-15 and 0.3 part of Potassium Persulphate again, under the normal temperature with rotating speed be 600 rev/mins stir 30 minutes after, obtain involucrum polymerization pre-emulsion; Drip the involucrum polymerized emulsion in the microcapsule capsule-core, keep the capsule-core temperature, the dropping time is 3 hours, is warming up to 70 ℃ after dropwising and continues to stir end reaction after 1.5 hours; Be cooled to and add ammoniacal liquor after the room temperature to regulate the pH value be 8, add 45 part 10% the adipic dihydrazide aqueous solution then, stir; Promptly obtain capsule of nano type aqueous color paste after removing small amount of impurities with 0.22 μ m millipore filtration at last.
One embodiment of the present invention are: in step 1), described emulsifying agent is sodium lauryl sulphate or peregal 0-15.
One embodiment of the present invention are: in step 1), described pH value conditioning agent is a sodium bicarbonate.
One embodiment of the present invention are: in step 1), described linking agent is Vinylstyrene or 1,4 butanediol diacrylate.
One embodiment of the present invention are: in step 1), described hydrophobic dyestuff is that anthraquinone type or azo class orchil, anthraquinone type or pyrazolone are yellow dyes, anthraquinone type green colouring material, anthraquinone type or phthalocyanines blue dyes.
One embodiment of the present invention are: in step 1), described droplet nucleation promotor is that number-average molecular weight is 20,000～70,000 polystyrene powder.
One embodiment of the present invention are: in step 1), but the hindered amine as light stabilizer that described response type photostabilizer is copolyreaction.
The invention has the beneficial effects as follows:
1, at first, microcapsule capsule-core of the present invention has been realized hydrophobic dyestuff and the mortise of nanometer polymer particle matrix under the non covalent bond condition wherein.
2, secondly; involucrum polyreaction of the present invention is a cyst wall for the polymer shell that the microcapsule capsule-core makes up protectiveness; strengthened dyestuff set stability in the nanometer polymer microballoon; intercept the direct infringement of outside oxygen, ultraviolet ray, chemical reagent etc., thereby further strengthened thermostability and fast light/marquis's property of product.
3, the present invention obtains the colored filter mill base be particularly useful for high performance textile inkjet printing coating ink, color inkjet printing ink and be applied to make liquid-crystal display, also can be applicable to water color ink and pigment coloration etc.
4, the present invention is a kind of high performance red, yellow, green and blue capsule of nano type aqueous color paste.
Description of drawings
Fig. 1 is TEM (transmission electron microscope) figure of the capsule of nano type aqueous color paste particle of redness.
Fig. 2 is TEM (transmission electron microscope) figure of xanchromatic capsule of nano type aqueous color paste particle.
Fig. 3 is TEM (transmission electron microscope) figure of the capsule of nano type aqueous color paste particle of green.
Fig. 4 is TEM (transmission electron microscope) figure of the capsule of nano type aqueous color paste particle of blueness.
Embodiment
The testing tool that the present invention adopts is as follows: (Lambda 20 for ultraviolet-visual spectrometer, Perkin Elmer), photon correlation spectrometer (Zetasizer Nano S, Malvern Instruments) median size (ZAve) and the size distribution (polydispersity index PDI) of mensuration nano-coloring material, 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, and NDJ-1 type rotational viscosimeter (the Shanghai flat scientific instrument of perseverance company) is measured the rotation viscosity.
In addition, the analysis test method of the present invention's employing is as follows:
1) the stability in storage investigation method of capsule of nano type aqueous color paste: sample left standstill under room temperature 90 days, observed flocculation, throw out etc. whether occur, and nothing flocculation and throw out then are evaluated as outstanding after 90 days;
2) the present invention to mill base fast light/comparative evaluation's method of marquis's property: at first capsule of nano type mill base 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 capsule of nano type aqueous color paste 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 30,000luxes, keep the colour film heating temperature 60～80 ℃ and relative humidity 30～50%.Then sample is passed through
The desk-top colourimeter of X E (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 146 or azo class C.I. solvent red H, the anthraquinone type yellow dyes is that pyrazolone is C.I. solvent yellow 93 or C.I. solvent yellow 16 3, the anthraquinone type green colouring material is C.I. solvent green 3 or C.I. solvent green 28, and the anthraquinone type blue dyes is C.I. solvent blue 58, C.I. solvent blue 97 or phthalocyanines C.I. solvent blue 67; But the piperidines of copolyreaction is a hindered amine as light stabilizer is GW-628 (Shanxi Province chemical research institute) or HA-R100 (atropic chemistry); Emulsifying agent peregal 0-15.
Specific embodiment 1:
1) mini-emulsion polymerization prepared in reaction capsule of nano capsule-core
0.65g sodium lauryl sulphate and 0.1g sodium bicarbonate are dissolved in the beaker that the 100g deionized water is housed, as water; 16g vinylbenzene, 2g methyl methacrylate and the 1.5g Vinylstyrene of removing stopper in advance with the washing of 5% white liquor, be added in another beaker, add 1.3g C.I. solvent red 146,0.16g droplet nucleation promotor and 0.08g response type photostabilizer 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 15 minutes earlier, inject the aqueous solution that the 0.16g Potassium Persulphate is dissolved in the 5g deionized water with syringe when rising to 60 ℃, the beginning initiated polymerization, remain under 65 ℃ of constant temperature and reacted 1.5 hours, obtain the microcapsule capsule-core;
2) the involucrum polyreaction prepares cyst wall
Take by weighing 16 parts of butyl acrylates, 7 parts of methyl methacrylates, 3 parts of hydroxyethyl methylacrylates and 5 parts of diacetone-acryloamide(DAA)s, add and be equipped with in the beaker of 25 parts of deionized waters, add 0.3 part of emulsifier sodium lauryl sulfate, 0.6 part of emulsifying agent peregal 0-15 and 0.3 part of Potassium Persulphate again, under the normal temperature with rotating speed be 600 rev/mins stir 30 minutes after, obtain involucrum polymerization pre-emulsion; Drip the involucrum polymerized emulsion in the microcapsule capsule-core, keep the capsule-core temperature, the dropping time is 3 hours, is warming up to 70 ℃ after dropwising and continues to stir end reaction after 1.5 hours.Be cooled to and add ammoniacal liquor after the room temperature to regulate the pH value be 8, add 45 part 10% the adipic dihydrazide aqueous solution then, stir.Promptly obtain capsule of nano type aqueous color paste after removing small amount of impurities with 0.22 μ m millipore filtration at last.
The final red nano microcapsule-type aqueous color paste that obtains shows good aqueous dispersion character (seeing Table 1), relatively more corresponding dyestuff has the fast light/marquis's property (seeing Table 2) that promotes greatly; Can find that from the TEM figure of Fig. 1 the mill base particle has made up fairly perfect microcapsule structure.
Specific embodiment 2:
1) mini-emulsion polymerization prepared in reaction capsule of nano capsule-core
0.5g sodium lauryl sulphate and 0.1g sodium bicarbonate are dissolved in the beaker that the 100g deionized water is housed, as water; The 16g vinylbenzene, 2g methyl methacrylate and the 1.2g 1 that remove stopper in advance with the washing of 5% white liquor, the 4-butylene glycol diacrylate, be added in another beaker, add 1.0g C.I. solvent red H, 0.16g droplet nucleation promotor and 0.08g response type photostabilizer HA-R100 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 12 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 15 minutes earlier, inject the aqueous solution that the 0.16g Potassium Persulphate is dissolved in the 5g deionized water with syringe when rising to 60 ℃, the beginning initiated polymerization, remain under 65 ℃ of constant temperature and reacted 1.5 hours, obtain the microcapsule capsule-core;
2) the involucrum polyreaction prepares cyst wall
Take by weighing 13 parts of butyl acrylates, 5 parts of methyl methacrylates, 2.5 parts of methacrylic acids and 4 parts of diacetone-acryloamide(DAA)s, add and be equipped with in the beaker of 25 parts of deionized waters, add 0.25 part of emulsifier sodium lauryl sulfate, 0.5 part of emulsifying agent peregal 0-15 and 0.25 part of ammonium persulphate again, under the normal temperature with rotating speed be 600 rev/mins stir 30 minutes after, obtain involucrum polymerization pre-emulsion; Drip the involucrum polymerized emulsion in the microcapsule capsule-core, keep the capsule-core temperature, the dropping time is 2.5 hours, is warming up to 70 ℃ after dropwising and continues to stir end reaction after 1.5 hours.Be cooled to and add ammoniacal liquor after the room temperature to regulate the pH value be 8, add 36 part 10% the adipic dihydrazide aqueous solution then, stir.Promptly obtain capsule of nano type aqueous color paste after removing small amount of impurities with 0.22 μ m millipore filtration at last.
Specific embodiment 3:
The characteristics of present embodiment are: according to embodiment 1, dyestuff is a 1.5g C.I. solvent yellow 93 in the reaction of change mini-emulsion polymerization, and all the other prescriptions are identical with technology.The final Yellow nanometer microcapsule-type aqueous color paste that obtains shows good aqueous dispersion character (seeing Table 1), relatively more corresponding dyestuff has the fast light/marquis's property (seeing Table 2) that promotes greatly; Can find that from the TEM figure of Fig. 2 the mill base particle has made up fairly perfect microcapsule structure.
Specific embodiment 4:
The characteristics of present embodiment are: according to embodiment 2, dyestuff is a 1.2g C.I. solvent yellow 16 3 in the reaction of change mini-emulsion polymerization, and all the other prescriptions are identical with technology.
Specific embodiment 5:
The characteristics of present embodiment are: according to embodiment 1, dyestuff is a 0.7g C.I. solvent green 3 in the reaction of change mini-emulsion polymerization, and all the other prescriptions are identical with technology.The final Preen nono microcapsule-type aqueous color paste that obtains shows good aqueous dispersion character (seeing Table 1), relatively more corresponding dyestuff has the fast light/marquis's property (seeing Table 2) that promotes greatly; Can find that from the TEM figure of Fig. 3 the mill base particle has made up fairly perfect microcapsule structure.
Specific embodiment 6:
The characteristics of present embodiment are: according to embodiment 2, dyestuff 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.
Specific embodiment 7:
The characteristics of present embodiment are: according to embodiment 1, dyestuff is a 2.0g C.I. solvent blue 58 in the reaction of change mini-emulsion polymerization, and all the other prescriptions are identical with technology.The final blue capsule of nano type aqueous color paste that obtains shows good aqueous dispersion character (seeing Table 1), relatively more corresponding dyestuff has the fast light/marquis's property (seeing Table 2) that promotes greatly; Can find that from the TEM figure of Fig. 4 the mill base particle has made up fairly perfect microcapsule structure.
Specific embodiment 8:
The characteristics of present embodiment are: according to embodiment 2, dyestuff is a 1.3g C.I. solvent blue 67 in the reaction of change mini-emulsion polymerization, and all the other prescriptions are identical with technology.
Comparative example 1,3,5 and 7 be respectively according to the present invention to mill base fast light/colour film of redness, yellow, green and the blue dyes of the preparation of comparative evaluation's method of marquis's property.As follows: table 1 is typical capsule of nano type aqueous color paste essential property contrast table.Table 2 is typical capsule of nano type aqueous color paste and fast light/marquis's property comparison sheet of the colour film of corresponding dyestuff preparation.
The typical capsule of nano type aqueous color paste essential property contrast table of table 1
Fast light/marquis's property comparison sheet of the colour film that the typical capsule of nano type aqueous color paste of table 2 and corresponding dyestuff prepare
| Sample | Aberration (Δ E) | Sample | Aberration (Δ E) |
| Embodiment 1 | 2.68 | Embodiment 5 | 1.51 |
| Comparative Examples 1 | 9.04 | Comparative Examples 5 | 8.65 |
| Embodiment 3 | 0.71 | Embodiment 7 | 3.56 |
| Comparative Examples 3 | 3.85 | Comparative Examples 7 | 11.52 |
The present invention has following features:
1, at first, making the nanometer polymer microballoon that is rich in dyestuff by the mini-emulsion polymerization reaction is the capsule-core of capsule of nano. Hydrophobic dyestuff existence in the microcapsules capsule-core of the present invention is: the dyestuff that all is dissolved with higher concentration in the miniemulsion monomer droplet as nano-reactor, when polymerisation is carried out, the dye molecule of small amount is owing to the sucking action that is subjected to the cross-linked macromolecular chain is attached on the macromolecular chain, and more dyestuff is then because the inside that dyestuff in the polymerization process and polymerization single polymerization monomer as solvent are separated and form dyestuff gathering phase and then embed big molecular coil. The crosslinked of polymer can greatly reduce its free volume and cause more closely polymer outside, dye molecule and dyestuff assembled mutually motion/migration play significant inhibition and barrier effect. Microcapsules capsule-core of the present invention has been realized hydrophobic dyestuff and the strong bonded of nanometer polymer particle matrix under the non-covalent bond condition wherein.
2, the involucrum polymerisation is cyst wall for the polymer shell that the microcapsules capsule-core makes up protectiveness; strengthened dyestuff set stability in the nanometer polymer microballoon; intercept the direct infringement of outside oxygen, ultraviolet ray, chemical reagent etc., thereby further strengthened heat endurance and fast light/marquis's property of product. By selecting self film and the ambient self-crosslinking characteristic of the realization mill bases such as soft or hard monomer ratio, self-cross linking monomer in the involucrum polymerisation. In addition, the reaction monomers such as hydrophilic methyl methacrylate and water miscible hydroxyethyl methacrylate can realize the surface modification of capsule-core, thereby obtain excellent storage stability.
3, the nano microcapsule water-based color paste of the present invention's acquisition is through a series of sign and test, comprise the average grain diameter of mill base particle and the storage stability investigation of particle size distribution measuring, Zeta potential mensuration, surface tension test, rotation viscosity measurement and aqueous color paste, also its fast light/marquis's property is compared test. The result of sign and analytical test shows that nano-coloring material aqueous dispersions of the present invention has excellent aqueous dispersion character: average grain diameter is less than 100nm, and the particle size dispersion index is less than 0.09; Greater than the high surfaces tension force of 45mN/m, less than the low rotation viscosity of 1.5cP, less than-high the Zeta potential of 52mV and outstanding storage stability, the dyestuff that uses than correspondence has greatly improve fast light/marquis's property. The colored filter mill base that this capsule of nano type mill base is particularly useful for high performance textile inkjet printing coating ink, color inkjet printing ink and is applied to make liquid crystal display also can be applicable to water color ink and pigment coloration etc.
Claims (7)
1. the preparation method of a capsule of nano type aqueous color paste is characterized in that may further comprise the steps, and wherein related material is represented with mass parts:
1) mini-emulsion polymerization prepared in reaction capsule of nano capsule-core
0.4～1 part of emulsifying agent and 0.06～0.3 part of pH value conditioning agent sodium bicarbonate are dissolved in the beaker that 100 parts of deionized waters are housed, as water; Removing 12～30 parts of vinylbenzene of stopper, 1～5 part of methyl methacrylate and 0.5～3 part of linking agent with the washing of 5% caustic-soda aqueous solution 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 20～30 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 10～20 minutes earlier, inject the aqueous solution that 0.05～0.3 part of Potassium Persulphate is dissolved in 3～8 parts of deionized waters with syringe when rising to 55～60 ℃, the beginning initiated polymerization, remain on 62～66 ℃ of following stirring reactions 1～2 hour, and obtained the microcapsule capsule-core;
2) the involucrum polyreaction prepares cyst wall
Take by weighing 12～50 parts of butyl acrylates, 6～30 parts of methyl methacrylates, 1～5 part of hydroxyethyl methylacrylate or methacrylic acid and 3～10 parts of diacetone-acryloamide(DAA)s, add and be equipped with in the beaker of 20～50 parts of deionized waters, add 0.2～0.6 part of emulsifier sodium lauryl sulfate, 0.4～1.2 part of emulsifying agent peregal 0-15 and 0.1～0.8 part of Potassium Persulphate or ammonium persulphate again, under the normal temperature with rotating speed be 300～900 rev/mins stir 30～60 minutes after, obtain involucrum polymerization pre-emulsion; Drip the involucrum polymerized emulsion in the microcapsule capsule-core, keep the capsule-core temperature, the dropping time is 2.5～3 hours, guarantees with starvation reinforcedly, is warming up to 68～73 ℃ after dropwising and continues stirring reaction down and finishes after 1～2 hour to react; Be cooled to and add ammoniacal liquor after the room temperature to regulate the pH value be 6～8, add 10～50 part 10% the adipic dihydrazide aqueous solution then, stir; Promptly obtain capsule of nano type aqueous color paste after removing small amount of impurities with 0.22 μ m millipore filtration at last.
2. the preparation method of a kind of capsule of nano type aqueous color paste according to claim 1 is characterized in that: this preparation method carries out according to the following steps, below all represents with mass parts:
1) mini-emulsion polymerization prepared in reaction capsule of nano capsule-core
0.65 part of emulsifying agent and 0.1 part of pH value conditioning agent sodium bicarbonate are dissolved in the beaker that 100 parts of deionized waters are housed, as water; Removing 16 parts of vinylbenzene of stopper, 2 parts of methyl methacrylates and 1.5 parts of linking agents with the washing of 5% white liquor in advance, be added in another beaker, add 1.3 parts of hydrophobic dyestuffs, 0.16 part of droplet nucleation promotor and 0.08 part of response type photostabilizer 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 250m l four-hole boiling flask that is connected to stirring, thermometer, prolong and nitrogen tube, heat up after feeding nitrogen deoxygenation in 15 minutes earlier, inject the aqueous solution that 0.16 part of Potassium Persulphate is dissolved in 5 parts of deionized waters with syringe when rising to 60 ℃, the beginning initiated polymerization, remain under 65 ℃ of constant temperature and reacted 1.5 hours, obtain the microcapsule capsule-core;
2) the involucrum polyreaction prepares cyst wall
Take by weighing 16 parts of butyl acrylates, 7 parts of methyl methacrylates, 3 parts of hydroxyethyl methylacrylates and 5 parts of diacetone-acryloamide(DAA)s, add and be equipped with in the beaker of 25 parts of deionized waters, add 0.3 part of emulsifier sodium lauryl sulfate, 0.6 part of emulsifying agent peregal 0-15 and 0.3 part of Potassium Persulphate again, under the normal temperature with rotating speed be 600 rev/mins stir 30 minutes after, obtain involucrum polymerization pre-emulsion; Drip the involucrum polymerized emulsion in the microcapsule capsule-core, keep the capsule-core temperature, the dropping time is 3 hours, is warming up to 70 ℃ after dropwising and continues to stir end reaction after 1.5 hours; Be cooled to and add ammoniacal liquor after the room temperature to regulate the pH value be 8, add 45 part 10% the adipic dihydrazide aqueous solution then, stir; Promptly obtain capsule of nano type aqueous color paste after removing small amount of impurities with 0.22 μ m millipore filtration at last.
3. the preparation method of a kind of capsule of nano type aqueous color paste according to claim 1 and 2 is characterized in that: in step 1), described emulsifying agent is sodium lauryl sulphate or peregal 0-15.
4. the preparation method of a kind of capsule of nano type aqueous color paste according to claim 1 and 2 is characterized in that: in step 1), described linking agent is Vinylstyrene or 1,4 butanediol diacrylate.
5. the preparation method of a kind of capsule of nano type aqueous color paste according to claim 1 and 2, it is characterized in that: in step 1), described hydrophobic dyestuff is that anthraquinone type or azo class orchil, anthraquinone type or pyrazolone are yellow dyes, anthraquinone type green colouring material, anthraquinone type or phthalocyanines blue dyes.
6. the preparation method of a kind of capsule of nano type aqueous color paste according to claim 1 and 2 is characterized in that: in step 1), described droplet nucleation promotor is that number-average molecular weight is 20,000～70,000 polystyrene powder.
7. the preparation method of a kind of capsule of nano type aqueous color paste according to claim 1 and 2 is characterized in that: in step 1), but the hindered amine as light stabilizer that described response type photostabilizer is copolyreaction.
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