CN101492584A - Black nano-water dispersible pigment dispersion using acrylic acid copolymer - Google Patents
Black nano-water dispersible pigment dispersion using acrylic acid copolymer Download PDFInfo
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- CN101492584A CN101492584A CNA2008101875749A CN200810187574A CN101492584A CN 101492584 A CN101492584 A CN 101492584A CN A2008101875749 A CNA2008101875749 A CN A2008101875749A CN 200810187574 A CN200810187574 A CN 200810187574A CN 101492584 A CN101492584 A CN 101492584A
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Abstract
A black nano water dispersible pigment dispersion liquid using acrylic copolymer is characterized by consisting of black pigment C.I.P.B.7, acrylic copolymers dispersant, bactericide and de-ionized water; wherein, the proportion between the black pigment and the dispersant is controlled within the range of 0.5-3. The preparation method comprises the steps: the dispersant and the de-ionized water are mixed in a container to be stirred and then added with the black pigment; the mixed solution is cut for 0.5-8h by a high speed shearing machine and then is ground and dispersed in a circulating way; granularity detection is carried out every 15min until the grain diameter of the dispersion liquid reaches the requirement. The invention has the advantages that the water dispersible pigment dispersion liquid has good dispersibility and storage stability; black pigment cluster is mechanically shattered to be smaller, so that the dispersant can be anchored and fixed on the pigment granules, thus preventing the pigment granules agglomerating together. The stability of the prepared pigment dispersion liquid is enhanced.
Description
(1) technical field:
The present invention relates to a kind of dispersible pigment dispersion, black nano-water dispersible pigment dispersion of particularly a kind of use acrylic copolymer that is used for the ink-jet field and preparation method thereof.
(2) background technology:
The market share that present black water paint ink with the black pigment preparation accounts for ink-jet printing ink is very big, the black water paint ink is used in general text printing more, even because its printing surface of black water paint ink print text file has water, ink also can be spread and sunk in hardly and be dyed paper; Simultaneously the text photostabilization printed of black pigment ink is strong, is difficult for fading, so can prolonged preservation; Again because the black pigment particle rests on paper surface in the ink, can the infiltrate paper, can realize duplex printing, save and print cost.And the black dyes ink was performed poor at this three face always in the past, so the black water paint ink is progressively substituting the black dye ink.
Black nano-water dispersible pigment dispersion is the key of preparation black water paint ink, but will expect that the good black nano-water dispersible pigment dispersion of dispersiveness, storage stability is by no means easy.Compare with general pigment dyestuff, the very tiny and surperficial oleophylic of the particle of black pigment, bad dispersibility in water obtains comparatively difficulty of good dispersion, so black nano-water dispersible pigment dispersion very easily goes wrong in preservation and use.In general, the mechanism of microcosmic particle stably dispersing can be divided into two kinds: the one, and electrocharge effect, electrocharge effect are the electric charges that utilizes the black pigment surface to exist, and make between the black pigment particle and produce electrical charge rejection, and the interparticle reunion of black pigment is alleviated; The 2nd, space steric effect.Space steric effect is to utilize the method for chemistry or physics to make the sterically hindered big segment of black pigment surface anchoring, utilizes the segmental space steric effect, and the interparticle reunion of black pigment is alleviated.If with enough mechanical energy the black pigment aggregate is smashed for a short time, allow dispersion agent be anchored at the surface of granules of pigments, prevent that granules of pigments from reuniting each other, so prepared dispersible pigment dispersion stability increases.
Chinese patent CN 1803945A report adopts 20000 pairs of black pigments of dispersion agent Solsperse to carry out the sand milling dispersion and the preparation black nano-water dispersible pigment dispersion, the gained dispersion liquid is through behind the three-stage filtration, the median size of dispersion liquid is between 110 ~ 125nm, but not relevant this black nano-water dispersible pigment dispersion estimation of stability.
(3) summary of the invention:
The objective of the invention is to design a kind of black nano-water dispersible pigment dispersion that uses acrylic copolymer and preparation method thereof, it is the good novel dispersion liquid of a kind of dispersiveness, storage stability.
Technical scheme of the present invention: a kind of black nano-water dispersible pigment dispersion that uses acrylic copolymer is characterized in that it is made up of black pigment C.I.P.B.7, acrylic copolymer class dispersion agent, sterilant and deionized water; Wherein the weight percent of black pigment C.I.P.B.7 is 3～30%, and the weight percent of dispersion agent is 5～50%, and the weight percent of sterilant is 0.2%, and surplus is a deionized water; Said acrylic copolymer class dispersion agent is selected the EDPLAN 482 or the EDPLAN 480 of Munzing Chemie Gmbh company for use; The ratio of said black pigment and dispersion agent should be controlled between 0.5～3.
The weight percent preferred 8～15% that above-mentioned said black pigment accounts for the dispersion liquid gross weight.
Above-mentioned said acrylic copolymer class dispersion agent accounts for the weight percent preferred 9.2 ~ 17.3% of dispersion liquid gross weight.
Between the ratio preferred 1.1～1.8 of above-mentioned said black pigment and dispersion agent.
Above-mentioned said black pigment is chosen wherein a kind of among the Raven 3500 of the Special black 4 of MA-7, the MA100 of Mongul-L, the R400R of Cabot (Cabot) company or R330R, Mitsubishi Chemical (Mitsubishi Chemical Corporation) company or #40, Degussa (Degussa) company and Colombia's chemistry (Columbian Chemical) company.
Above-mentioned said acrylic copolymer class dispersion agent contains hydrophilic segment and hydrophobic segment.
Above-mentioned said sterilant is the benzisothiazole letones, selects the Nipacide BIT-20 of Clariant (Clariant) company for use.
The effective content of above-mentioned said dispersion agent is got the reference numerals on this commercial dispersants product description; It is fixed that the consumption of this dispersion agent comes according to the specific surface area of black pigment.
A kind of preparation method who uses the black nano-water dispersible pigment dispersion of acrylic copolymer is characterized in that comprising the preparation of dispersion liquid and the preparation of ink, wherein:
(1) preparation of dispersion liquid may further comprise the steps:
1. dispersion agent and deionized water are mixed in the container according to aforementioned proportion, and stir;
2. add black pigment in proportion, fully wetting;
3. with high-speed shearing machine with the 2. dispersion liquid high speed shear 0.5～8.0 hour of gained of step, rotating speed is 1000～10000rpm, shears and finishes back placement 10.0～20.0 minutes;
4. with step 3. the shearing dispersion liquid of gained pump into and grind dispersion in the shredder;
5. with step 4. in the dispersion liquid of shredder discharge port gained enter the stock chest of shredder, pump into shredder once more and carried out circular grinding 0.5～24.0 hour;
6. in the process of lapping, adopted the LB-550 type dynamic laser look particle size analyzer that looses to carry out granularity Detection every 15 minutes, reach requirement up to the particle diameter of dispersion liquid.
The process of the dispersion liquid formulate ink that (two) makes is: get the 6. prepared dispersion liquid 10～50% of above-mentioned steps by weight percentage, wetting Agent for Printing Inks 5～30%, tensio-active agent 0.1～2% with the surplus deionized water, make ink for ink-jet print;
The said ink of making can be used in the Detection of Stability under the regular constant temperature of dispersion liquid.
Above-mentioned steps is 1.-3. for shearing dispersion steps: wherein mainly to act on be to make the dispersion agent dispersion and emulsion even to the high speed shear of step in 3., smash in the part black pigment than macroparticle, but its effect of overlong time is no longer remarkable, so preferred 1.0～2.0 hours of shear time.
Above-mentioned steps is 4.-6. for grinding dispersion steps: wherein the shredder of step in 4. be pin bar type shredder, ball mill and novel nano performance shredder-
A kind of among the-MILL NPM, grinding medium adopts a kind of in zirconium pearl, zirconium oxide bead and the high-performance silicic acid zirconium pearl, and mean diameter is between 0.05～1.00mm; Preferred rotating speed is pin bar type shredder and the zirconium oxide bead of diameter between 0.05～0.20mm of 600～4000rpm; The grinding purposes of said step in 4. is to make the particle diameter of black nano-water dispersible pigment dispersion continue to reduce, but prolongation along with milling time, its particle diameter lowering speed will be far smaller than initial 1.0～3.0 hours, and grinding effect is no longer remarkable, so preferred 1.0～3.0 hours of milling time; The discharge port temperature of said step in 5. is controlled between 20～40 ℃; 6. said step is the pigment granularity Detection.
The step of the pigment granularity Detection of above-mentioned said step in 6. is:
A, take out a testing sample with dropper, put into the test tube that specification is 18mm * 180mm, add deionized water height to 1/2 test tube height, vibration shakes up;
B, the sample that will dilute are put into the ultrasonic 2mins of ultrasonic instrument, and frequency setting is 40kHz * 80%, and temperature is 25 ℃;
C, put into the sample of ultrasonic mistake respectively in 3 cuvettes, liquid level is lower than cuvette outer 0.5cm;
LB-550 application program on d, the double-click computer desktop;
E, open the lid of LB-550 type dynamic light scattering nano particle size analyser gently, in sample pool, put into the cuvette that fills sample;
F, click Temp Panel, treat that temperature controls to 25 ℃ after, click Meas.Panel, Measurement Panel appears on the screen and after, click Measure, begin test;
G, the test of wait machine finish record data.The particle diameter of each sample is the weighted mean of three observed values.
Superiority of the present invention is: the present invention has good dispersiveness and storage stability, smash the black pigment aggregate little by machinery, allow dispersion agent be anchored at the surface of granules of pigments, prevent that granules of pigments from reuniting each other, prepared dispersible pigment dispersion stability increases.
(4) embodiment:
In this case about the explanation of the effective content of dispersion agent: the effective content of dispersion agent is got the reference numerals on this commercial dispersants product description, with the EDPLAN 482 of Munzing Chemie Gmbh company.EDPLAN 482 aqueous high molecular dispersion agents are example, and its effective content is 85%.It is fixed that the consumption of this dispersion agent comes according to the specific surface area of black pigment.The related black pigment of the present invention adopts the MA-7 of Mitsubishi Chemical (Mitsubishi ChemicalCorporation), and its initial particle is 24nm, specific surface area 115m2/g.
For the testing product quality, following experiment testing process to product property is arranged:
Month stability experiment of normal temperature:
Testing sample is put into Glass Containers, in the environment of constant temperature (25 ℃) constant humidity (35%RH), placed one month, measure the change of granularity situation of a month front and back sample.
" part " among the embodiment by weight.
Embodiment 1
Black pigment MA-7 with 8 parts of Mitsubishi Chemicals (Mitsubishi Chemical Corporation), the EDPLAN 482 of 8 parts of Munzing Chemie Gmbh companies, its active constituent content 85%, 0.2 mixing with the high speed shear agitator, the sterilant Nipacide BIT-20 of part Clariant (Clariant) company and 83.8 parts of deionized waters after evenly, must shear dispersion liquid in 1 hour, shearing dispersion liquid to 300g ground 1 hour in 0.14L volumetrical shredder again, obtained water dispersible pigment dispersion.The ratio of pigment and dispersion agent is 1.18: 1.The water dispersible pigment dispersion of preparation is carried out a month stability experiment at normal temperatures.
Comparative example 1-2 represents to prepare the example of the dispersion liquid outside the application of the present invention.
Comparative example 1
Black pigment MA-7 with 8 parts of Mitsubishi Chemicals (Mitsubishi Chemical Corporation), 0.2 mixing with the high speed shear agitator, the sterilant Nipacide BIT-20 of part Clariant (Clariant) company and 91.8 parts of deionized waters after evenly, must shear dispersion liquid in 1 hour, shearing dispersion liquid to 300g ground 1 hour in 0.14L volumetrical shredder again, obtained water dispersible pigment dispersion.The water dispersible pigment dispersion of preparation is carried out a month stability experiment at normal temperatures.
Comparative example 2
Black pigment MA-7 with 8 parts of Mitsubishi Chemicals (Mitsubishi Chemical Corporation), 6.9 the dispersion agent Solsperse 20000 of part road Bo Run (Lubrizol) company, its active constituent content 100%, 0.2 mixing with the high speed shear agitator, the sterilant Nipacide BIT-20 of part Clariant (Clariant) company and 84.9 parts of deionized waters after evenly, must shear dispersion liquid in 1 hour, shearing dispersion liquid to 300g ground 1 hour in 0.14L volumetrical shredder again, obtained water dispersible pigment dispersion.The ratio of pigment and dispersion agent is 1.16: 1.The water dispersible pigment dispersion of preparation is carried out a month stability experiment at normal temperatures.The black nano-water dispersible pigment dispersion prescription of table 1 embodiment 1 and comparative example 1～2
And the ratio of pigment and dispersion agent
| Dispersion agent | Black pigment amount/w% | Disperse dosage/w% | Pigment: dispersion agent | |
| Comparative example 1 | Do not have | 8 | 0 | NA |
| Comparative example 2 | Solsperse 20000 | 8 | 6.9 | 1.16∶1 |
| Embodiment 1 | Edaplan 482 | 8 | 8 | 1.18∶1 |
The particle diameter D50 (nm) of black nano-water dispersible pigment dispersion grinding back and the changing conditions after January under table 2 normal temperature
| Dispersion agent | Grind the back particle diameter | Normal temperature particle diameter after following January | The change of size rate | |
| Comparative example 1 | Do not have | NA | NA | NA |
| Comparative example 2 | Solsperse 20000 | Layering | NA | NA |
| Embodiment 1 | Edaplan 482 | 101.8 | 102.6 | 0.8％ |
Comparative example 1 is sheared the back gained and is sheared dispersion liquid and can not circulate and enter shredder and grind, and can not form stable dispersion liquid, the layering of gained dispersion liquid after comparative example 2 grinds.Embodiment 1 gained dispersion liquid D50 is all below 105nm, and storage stability is good in one month at normal temperatures.
Claims (10)
1. black nano-water dispersible pigment dispersion that uses acrylic copolymer is characterized in that it is made up of black pigment C.I.P.B.7, acrylic copolymer class dispersion agent, sterilant and deionized water; Wherein the weight percent of black pigment C.I.P.B.7 is 3～30%, and the weight percent of dispersion agent is 5～50%, and the weight percent of sterilant is 0.2%, and surplus is a deionized water; Said acrylic copolymer class dispersion agent is selected the EDPLAN 482 or the EDPLAN 480 of Munzing Chemie Gmbh company for use; The ratio of said black pigment and dispersion agent should be controlled between 0.5～3.
2. according to the said a kind of black nano-water dispersible pigment dispersion that uses acrylic copolymer of claim 1, it is characterized in that said black pigment accounts for the weight percent preferred 8～15% of dispersion liquid gross weight; Said acrylic copolymer class dispersion agent accounts for the weight percent preferred 9.2 ~ 17.3% of dispersion liquid gross weight.
3. according to the said a kind of black nano-water dispersible pigment dispersion that uses acrylic copolymer of claim 1, it is characterized in that between the ratio preferred 1.1～1.8 of said black pigment and dispersion agent.
4. according to the said a kind of black nano-water dispersible pigment dispersion that uses acrylic copolymer of claim 1, it is characterized in that black pigment chooses wherein a kind of among the Raven 3500 of the Special black 4 of MA-7, the MA100 of Mongul-L, the R400R of Cabot (Cabot) company or R330R, Mitsubishi Chemical (Mitsubishi Chemical Corporation) company or #40, Degussa (Degussa) company and Colombia's chemistry (Columbian Chemical) company.
5. according to the said a kind of black nano-water dispersible pigment dispersion that uses acrylic copolymer of claim 1, it is characterized in that said acrylic copolymer class dispersion agent contains hydrophilic segment and hydrophobic segment.
6. according to the said a kind of black nano-water dispersible pigment dispersion that uses acrylic copolymer of claim 1, it is characterized in that said sterilant is the benzisothiazole letones, select the Nipacide BIT-20 of Clariant (Clariant) company for use.
7. according to the said a kind of black nano-water dispersible pigment dispersion that uses acrylic copolymer of claim 1, the effective content that it is characterized in that said dispersion agent is got the reference numerals on this commercial dispersants product description; It is fixed that the consumption of this dispersion agent comes according to the specific surface area of black pigment.
8. a preparation method who uses the black nano-water dispersible pigment dispersion of acrylic copolymer is characterized in that comprising the preparation of dispersion liquid and the preparation of ink, wherein:
(1) preparation of dispersion liquid may further comprise the steps:
1. dispersion agent and deionized water are mixed in the container according to aforementioned proportion, and stir;
2. add black pigment in proportion, fully wetting;
3. with high-speed shearing machine with the 2. dispersion liquid high speed shear 0.5～8.0 hour of gained of step, rotating speed is 1000～10000rpm, shears and finishes back placement 10.0～20.0 minutes;
4. with step 3. the shearing dispersion liquid of gained pump into and grind dispersion in the shredder;
5. with step 4. in the dispersion liquid of shredder discharge port gained enter the stock chest of shredder, pump into shredder once more and carried out circular grinding 0.5～24.0 hour;
6. in the process of lapping, adopted the LB-550 type dynamic laser look particle size analyzer that looses to carry out granularity Detection every 15 minutes, reach requirement up to the particle diameter of dispersion liquid.
The process of the above-mentioned said dispersion liquid formulate ink that makes is: get the 6. prepared dispersion liquid 10～50% of above-mentioned steps by weight percentage, wetting Agent for Printing Inks 5～30%, tensio-active agent 0.1～2% with the surplus deionized water, make ink for ink-jet print;
(2) ink of making can be used in the Detection of Stability under the regular constant temperature of dispersion liquid.
9. said according to Claim 8 a kind of preparation method who uses the black nano-water dispersible pigment dispersion of acrylic copolymer, it is characterized in that said step is 1.-3. for shearing dispersion steps: wherein mainly to act on be to make the dispersion agent dispersion and emulsion even to the high speed shear of step in 3., smash in the part black pigment than macroparticle, but its effect of overlong time is no longer remarkable, so preferred 1.0～2.0 hours of shear time.
Above-mentioned steps is 4.-6. for grinding dispersion steps: wherein the shredder of step in 4. be pin bar type shredder, ball mill and novel nano performance shredder-
A kind of among the-MILL NPM, grinding medium adopts a kind of in zirconium pearl, zirconium oxide bead and the high-performance silicic acid zirconium pearl, and mean diameter is between 0.05～1.00mm; Preferred rotating speed is pin bar type shredder and the zirconium oxide bead of diameter between 0.05～0.20mm of 600～4000rpm; The grinding purposes of said step in 4. is to make the particle diameter of black nano-water dispersible pigment dispersion continue to reduce, but prolongation along with milling time, its particle diameter lowering speed will be far smaller than initial 1.0～3.0 hours, and grinding effect is no longer remarkable, so preferred 1.0～3.0 hours of milling time; The discharge port temperature of said step in 5. is controlled between 20～40 ℃; 6. said step is the pigment granularity Detection.
10. according to the said a kind of preparation method who uses the black nano-water dispersible pigment dispersion of acrylic copolymer of claim 9, it is characterized in that the step of the pigment granularity Detection during said step is 6. is:
A, take out a testing sample with dropper, put into the test tube that specification is 18mm * 180mm, add deionized water height to 1/2 test tube height, vibration shakes up;
B, the sample that will dilute are put into the ultrasonic 2mins of ultrasonic instrument, and frequency setting is 40kHz * 80%, and temperature is 25 ℃;
C, put into the sample of ultrasonic mistake respectively in 3 cuvettes, liquid level is lower than cuvette outer 0.5cm;
LB-550 application program on d, the double-click computer desktop;
E, open the lid of LB-550 type dynamic light scattering nano particle size analyser gently, in sample pool, put into the cuvette that fills sample;
F, click Temp Panel, treat that temperature controls to 25 ℃ after, click Meas.Panel, Measurement Panel appears on the screen and after, click Measure, begin test;
G, the test of wait machine finish record data.The particle diameter of each sample is the weighted mean of three observed values.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101875749A CN101492584A (en) | 2007-12-28 | 2008-12-26 | Black nano-water dispersible pigment dispersion using acrylic acid copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710060598.3 | 2007-12-28 | ||
| CN200710060598 | 2007-12-28 | ||
| CNA2008101875749A CN101492584A (en) | 2007-12-28 | 2008-12-26 | Black nano-water dispersible pigment dispersion using acrylic acid copolymer |
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| CN101492584A true CN101492584A (en) | 2009-07-29 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062222A (en) * | 2015-07-24 | 2015-11-18 | 吴江市屯村颜料厂 | Pigment fast brilliant red BBC dispersion and preparation method therefor |
| CN106318030A (en) * | 2016-08-16 | 2017-01-11 | 湖南新力华纳米科技有限公司 | Environmentally-friendly pigment black ink color paste used for automatic digital laser printing and preparation method thereof |
-
2008
- 2008-12-26 CN CNA2008101875749A patent/CN101492584A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062222A (en) * | 2015-07-24 | 2015-11-18 | 吴江市屯村颜料厂 | Pigment fast brilliant red BBC dispersion and preparation method therefor |
| CN106318030A (en) * | 2016-08-16 | 2017-01-11 | 湖南新力华纳米科技有限公司 | Environmentally-friendly pigment black ink color paste used for automatic digital laser printing and preparation method thereof |
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