CN100372773C - Method for producing nano calcium carbonate particles for printing ink - Google Patents
Method for producing nano calcium carbonate particles for printing ink Download PDFInfo
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- CN100372773C CN100372773C CNB2003101229804A CN200310122980A CN100372773C CN 100372773 C CN100372773 C CN 100372773C CN B2003101229804 A CNB2003101229804 A CN B2003101229804A CN 200310122980 A CN200310122980 A CN 200310122980A CN 100372773 C CN100372773 C CN 100372773C
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- calcium carbonate
- acid
- temperature
- printing ink
- metal salt
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 66
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 38
- 239000002245 particle Substances 0.000 title claims abstract description 20
- 238000007639 printing Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 15
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 15
- 239000004571 lime Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000006071 cream Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 15
- 238000005255 carburizing Methods 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- -1 alkali metal salt Chemical class 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229960004418 trolamine Drugs 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 235000011147 magnesium chloride Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- 150000002016 disaccharides Chemical class 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000920 calcium hydroxide Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002932 luster Substances 0.000 abstract description 2
- 238000010899 nucleation Methods 0.000 abstract description 2
- 230000006911 nucleation Effects 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 24
- 244000089742 Citrus aurantifolia Species 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000021388 linseed oil Nutrition 0.000 description 4
- 239000000944 linseed oil Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention provides a manufacture method for nanometer class calcium carbonate particles for printing ink. In the present invention, proper crystal nucleus promoter is added in the initial stage of reaction, simultaneously, the crystal nucleation and the growth rate of each crystal face is conveniently regulated by controlling the flow quantity of carbon dioxide kiln gas and the concentration and the temperature of initial calcium hydroxide lime cream, and a dispersing agent is added when the carbonization rate reaches more than 80% so as to regulate the surface charge of the calcium carbonate particles and prevent the calcium carbonate particles from agglomerating so that the purpose of easily controlling the particle diameter and the shape of final products is achieved and the dispersibility of the final products can be obviously improved by proper surface treatment. The carburization reaction of the present invention releases heat, and naturally increases temperature so as to greatly reduce the energy consumption for reaching desired coating temperature and equipment and operation cost. Because the obtained cubical nanometer class calcium carbonate is generated at higher temperature, the surface energy density is low so that the present invention represents the product application characteristics of good luster and easy dispersion in the aspect of application.
Description
Technical field
The present invention relates to a kind of manufacture method of nanometer level calcium carbonate particle, specifically design the printing ink preparing nanometic particle of calcium carbonate, more particularly, relate to its particle diameter of a kind of nano particle and in 10～60nm scope, have the controlled average particle size particle size and the manufacture method of distribution thereof.
Technical background
Nano-calcium carbonate is meant the superfine powder of particle diameter less than 100nm, be widely used in fields such as rubber, plastics, high-grade paint, papermaking, high-grade printing ink, be the functional mineral filler of a kind of novel high-grade, thereby carry out at different application systems that surface modification treatment obtains high reactivity, dispersing property product good, that interface compatibility is good is the basic demand to nano-calcium carbonate.
Require transparent application scenario as flexographic ink, UV light-curable ink and four-colour chromatography printing ink etc., not only require the calcium carbonate granule divided by maximum granularity less than 40nm, and when being used for ink formulations, have the dispersive of being easy to characteristics.And translucent printing ink calcium is the kind of the most generally using in the resin type printing ink, has to be easy to disperse and good printability, is used to improve the flowability and the levelling property of printing ink.The preparation method commonly used of nano-calcium carbonate has continuous multistage spray carbonation method, hypergravity carborization, stirring tank carborization at present.Multistage spray carbonation method and hypergravity carborization all are to carry out the gas-liquid mass transfer reaction with liquid as disperse phase continuously, increase the gas-to-liquid contact area greatly, strengthened carbonization process microcosmic mix and the microcosmic mass transfer process, easily form a large amount of nucleus in initial reaction stage, can under comparatively high temps, produce nano-calcium carbonate; But continuously multistage spray carbonation method production efficiency is low, and energy consumption is big, and nozzle stops up easily, is difficult to guarantee the uniform distribution of droplet.The facility investment of hypergravity carborization is big, operation easier is bigger, and how this technology keeps in the lab scale process factor such as former strong field distribution to await further further investigation after amplifying.
The stirring tank carborization is the domestic and international at present extensively method of the production nano-calcium carbonate of employing, this method needs strict control carbonization temperature at 10～30 ℃ at whole carbonization process, and the generative process of lime carbonate is thermopositive reaction, therefore needs to adopt huge pressure cooling heat transferring system.The open CN1330039A of Chinese patent application has announced a kind of method that adopts mechanical stirring blended mode synthesis of nano lime carbonate at a lower temperature, then low temperature synthetic calcium carbonate suspension is heated to 45～95 ℃, add surface-modifying agent and handle, make the treated carbonates of 20～90nm; The open CN1332207A of Chinese patent application announced a kind of in 5～35 ℃ of carbonization temperature scopes the synthesis of nano calcium carbonate granule, the pattern that in carbonization process, adds crystalline form conditioning agent control calcium carbonate granule, add dispersion agent and regulate the calcium carbonate granule surface charge, then carburizing reagent synthetic calcium carbonate nano particulate suspension is warmed up between 60～90 ℃, carry out the surface with resinous acids such as rosin and coat processing, obtain between 15～40nm, specific surface area is greater than 35m
2/ g, oil-absorption(number) 40gDOP/100g CaCO
3The printing ink transparent nanometer calcium carbonate.
Because the nano-calcium carbonate that generates is easy to reunite, the calcium carbonate suspension that generally needs to generate is heated to 60～95 ℃, adds corresponding surface treatment agent again and coats processing, just can make the good luster of meeting the need of market, the product good with resin compatible.This shows that prior art is containing significant wastage to energy preparing the method for printing ink with transparent nanometer calcium carbonate and translucent lime carbonate.
Summary of the invention
The technical issues that need to address of the present invention provide the manufacture method of a kind of printing ink with nanometer level calcium carbonate particle, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention is such:
The inventive method adds suitable nucleus promotor according to the demand of different grain size products at the reaction initial period, with quantity and the controlled amount that reaches the initial reaction stage nucleus.According to nucleus free energy of formation in the crystallisation process greater than the thermodynamic principles of crystal growth free energy, simultaneously by controlling the flow of carbonic acid gas kiln gas, the concentration of initial calcium hydroxide milk of lime and temperature, regulate the growth velocity of crystalline nucleation and each crystal face easily, reach 80% at carbonation rate and add dispersion agent when above to regulate the calcium carbonate particles surface charge, prevent the reunion between the calcium carbonate granule, thereby the particle diameter and the pattern that reach the finished product are easy to control, can significantly improve the dispersing property of the finished product by suitable surface treatment.
Method of the present invention comprises the steps:
(1) nucleus being formed promotor adds in the lime cream soliquoid;
Said nucleus forms promotor and comprises EDTA and alkaline metal salt thereof, carboxylic acid inner complex, inorganic phosphate, hydroxyethyl di 2 ethylhexyl phosphonic acid, the an alkali metal salt of tartrate, oxalic acid, oxysuccinic acid, citric acid and above-mentioned acid, one or more mixtures in sulfuric acid and vitriol thereof, trolamine, disaccharides or the polysaccharide, optimization citric acid sodium, glucose, sucrose, sodium sulfate, trolamine;
The add-on that nucleus forms promotor is 0.7～5% of a gained lime carbonate quality, and temperature is 20～45 ℃.The weight concentration of lime cream soliquoid is suitable with 6～15%.
Lime cream soliquoid is to obtain like this: add unslaked lime and carry out digestion reaction in water, generate calcium hydroxide slurry, i.e. lime cream soliquoid.
(2) form in the lime cream soliquoid of promotor at the above-mentioned nucleus that added, feed carbon dioxide, preferably feed the carbonated volume percent and be 15～40% gas, its composition is similar to actual lime burner furnace gas mixture, and Ventilation Rate is 2～30m
3/ (h.m
3And be preferably under the whipped state and feed lime cream soliquoid).
(3) when carbonation rate to 80% is above, add dispersion agent;
Said dispersion agent comprises one or more mixtures in phosphoric acid salt, muriate, the sodium polyacrylate, wherein preferred sodium polyphosphate, magnesium chloride and zinc chloride, and add-on is 0.6～2.0% of a gained lime carbonate quality.
When the pH of suspension value reduces to 6.5～7.0, continue ventilation 10～20 minutes, stop ventilation then.The temperature rise of whole carbonization process nature is about 20～35 ℃, and the outlet temperature of reacting slurry reached 45～70 ℃ when carburizing reagent finished.
(4) finishing the back temperature in carburizing reagent is in 45～70 ℃ the calcium carbonate suspension, adding coating weight content is 5～15% the aqueous solution, said coating comprises one or more the mixture in sylvic acid and an alkali metal salt, hydrogenation modification sylvic acid and an alkali metal salt thereof or nilox resin acid and an alkali metal salt thereof, the consumption of coating counts 1.5～4% with lime carbonate, coating the treatment time is 1～2 hour, adopts conventional method to collect the printing ink nanometer level calcium carbonate particle then.
Synthetic and through coating the calcium carbonate particles of handling by aforesaid method carburizing reagent of the present invention, particle diameter is in 12～65nm scope and have controlled size distribution, is shaped as cube, and specific surface area is at 30～70m
2Can regulate between/the g, oil-absorption(number)＜37gDOP/100g product, and do not have agglomeration, can be applicable to offset printing, screen printing ink, UV curing inks, and require application scenarios such as transparent filling, enhancing, rheology modifying.
Characteristics of the present invention are to adopt above-mentioned specific technology, pressure cooling heat transferring system that must be not traditional in carbonization process not only, the carburizing reagent heat release heats up naturally, carburizing reagent finishes back calcium carbonate suspension temperature and reaches 45～70 ℃, greatly reduce to reach and coat temperature required energy expenditure, make equipment and process cost reduce greatly.And, obviously quickened carburizing reagent because the carburizing reagent heat release improves suspension temperature gradually, save the carburizing reagent time, thereby obviously improved the throughput of unit reactor volume.Another advantage of the inventive method is the generation of growing up of gained cube nanometer grade calcium carbonate under higher temperature, compare with traditional low-temp reaction, the calcium carbonate crystal that high temperature is grown up is fine and close more, surface energy density is lower, thereby shows better gloss and be easy to dispersive product application characteristics in application facet.
The said carbonation rate of the present invention is meant that the calcium hydroxide of calcium hydroxide cubage in the lime cream soliquoid of measuring according to the phenolphthalein indicator method has been converted into the mass percent of lime carbonate.
Description of drawings
Accompanying drawing 1 is the transmission electron microscope photo of embodiment 2 products, and scale is 20nm among the figure.
Accompanying drawing 2 is the transmission electron microscope photo of embodiment 3 products, and scale is 50nm among the figure.
Embodiment
Below by example the specific embodiment of the present invention is narrated, but embodiment does not limit protection scope of the present invention.
Embodiment 1
The starting temperature that adds 5 liters of concentration 6% (mass concentration) in 7 liters stirred autoclave is 36 ℃ a refining lime slurry, add 8.1g sucrose simultaneously, after stirring, the feeding carbon dioxide content is that the kiln gas of 15% (volumetric concentration) begins to carry out carburizing reagent, and the kiln gas flow is 25L/h.When carbonation rate to 80%, add the 2.8g sodium polyphosphate, continuing to ventilate to slurry pH is that to obtain temperature at 6.5 o'clock be 55 ℃ nano-calcium carbonate slip, adding in this slurry and containing sylvic acid 10.13g concentration is that 5% (weight concentration) temperature is 95 ℃ a sylvic acid saponification emulsion, stir, carry out 2h and coat activation treatment, with slip filtered while hot, washing, 90 ℃～100 ℃ are drying to obtain cube and class ball shaped nano transparent ink calcium.The main size distribution of this product is 20～40nm, and specific surface area is 45m
2/ g, oil-absorption(number) are 33gDOP/100gCaCO
3, and there is not agglomeration, the standard ink sample glossiness made from No. 3 stand linseed oil is good, transparency is high, degree of mobilization is 34mm.
The starting temperature that adds 5 liters of concentration 9% (mass concentration) in 7 liters stirred autoclave is 30 ℃ a refining lime slurry, add 20g sucrose and 10g trolamine simultaneously, after stirring, the feeding carbon dioxide content is that the kiln gas of 35% (volumetric concentration) begins to carry out carburizing reagent, and the kiln gas flow is 150L/h.When carbonation rate to 90%, add the 12g zinc chloride, continuing to ventilate to slurry pH is that to obtain temperature at 6.7 o'clock be 60 ℃ nano-calcium carbonate slip, adding in this slurry and containing nilox resin acid 24g concentration is that 7% (weight concentration) temperature is 90 ℃ a disproportionated rosin acid soap emulsion, stir, carry out 1h and coat activation treatment, with slip filtered while hot, washing, 90 ℃～100 ℃ are drying to obtain cube and class ball shaped nano transparent ink calcium.The main size distribution of this product is 10-25nm, and specific surface area is 60m
2/ g, oil-absorption(number) are 35gDOP/100gCaCO
3, and there is not agglomeration, the standard ink sample glossiness made from No. 3 stand linseed oil is good, transparency is high, degree of mobilization is 36mm.
Embodiment 3
The starting temperature that adds 5 liters of concentration 15% (mass concentration) in 7 liters stirred autoclave is 25 ℃ a refining lime slurry, add the 8g Trisodium Citrate simultaneously, after stirring, the feeding carbon dioxide content is that the kiln gas of 40% (volumetric concentration) begins to carry out carburizing reagent, and the kiln gas flow is 100L/h.When carbonation rate to 95%, add 5g zinc chloride and 5g magnesium chloride, continuing to ventilate to slurry pH is that to obtain temperature at 6.9 o'clock be 70 ℃ nano-calcium carbonate slip, adding in this slurry and containing nilox resin acid 30g concentration is that 15% (weight concentration) temperature is 80 ℃ a disproportionated rosin acid soap emulsion, stir, carry out 1h and coat activation treatment, with slip filtered while hot, washing, 90 ℃～100 ℃ are drying to obtain cube and class ball shaped nano translucent printing ink calcium.The main size distribution of this product is 40～60nm, and specific surface area is 38m
2/ g, oil-absorption(number) are 30gDOP/100gCaCO
3, and there is not agglomeration, the standard ink sample glossiness made from No. 3 stand linseed oil is good, present translucency, degree of mobilization is 27mm.
Embodiment 4
The starting temperature that adds 5 liters of concentration 12% (mass concentration) in 7 liters stirred autoclave is 30 ℃ a refining lime slurry, add the 8g Trisodium Citrate simultaneously, after stirring, the feeding carbon dioxide content is that the kiln gas of 30% (volumetric concentration) begins to carry out carburizing reagent, and the kiln gas flow is 150L/h.When carbonation rate to 95%, add the 8g magnesium chloride, continuing to ventilate to slurry pH is that to obtain temperature at 6.8 o'clock be 61 ℃ nano-calcium carbonate slip, by 2 the method implemented this slurry is coated activation and filtration, washing, drying treatment, promptly get cube and class ball shaped nano translucent printing ink calcium.The main size distribution of this product is 30～50nm, and specific surface area is 42m
2/ g, oil-absorption(number) are 33gDOP/100gCaCO
3, and there is not agglomeration, the standard ink sample glossiness made from No. 3 stand linseed oil is good, present translucency, degree of mobilization is 30mm.
Claims (8)
1. the manufacture method of a printing ink usefulness nanometer level calcium carbonate particle is characterized in that, comprises the steps:
(1) nucleus being formed promotor adds in the lime cream soliquoid;
Said nucleus forms promotor and comprises EDTA and alkaline metal salt thereof, carboxylic acid inner complex, inorganic phosphate, hydroxyethyl di 2 ethylhexyl phosphonic acid, the an alkali metal salt of tartrate, oxalic acid, oxysuccinic acid, citric acid and above-mentioned acid, one or more mixtures in sulfuric acid and vitriol thereof, trolamine, disaccharides or the polysaccharide;
(2) feeding carbon dioxide or feeding carbonated volume percent are 15～40% gas;
(3) when carbonation rate to 80% is above, add dispersion agent;
Said dispersion agent comprises one or more mixtures in phosphoric acid salt, muriate, the sodium polyacrylate;
When the pH of suspension value reduces to 6.5～7.0, continue ventilation 10～20 minutes, the outlet temperature of reacting slurry reached 45～70 ℃ when carburizing reagent finished;
(4) aqueous solution of adding coating, said coating comprises one or more the mixture in sylvic acid and an alkali metal salt, hydrogenation modification sylvic acid and an alkali metal salt thereof or nilox resin acid and an alkali metal salt thereof, adopts conventional method to collect the printing ink nanometer level calcium carbonate particle then.
2. method according to claim 1 is characterized in that, it is a kind of in Trisodium Citrate, glucose, sucrose, sodium sulfate or the trolamine that nucleus forms promotor.
3. method according to claim 1 is characterized in that, the add-on that nucleus forms promotor is 0.7～5% of a gained lime carbonate quality, and the temperature when forming nucleus in the promotor adding lime cream soliquoid is 20～45 ℃.
4. method according to claim 1 is characterized in that, the weight concentration of lime cream soliquoid is 6～15%.
5. method according to claim 1 is characterized in that dispersion agent comprises sodium polyphosphate, magnesium chloride and zinc chloride, and add-on is 0.6～2.0% of a gained lime carbonate quality.
6. method according to claim 1 is characterized in that, adding coating weight content is 5～15% the aqueous solution.
7. method according to claim 1 is characterized in that the consumption of coating counts 1.5～4% with lime carbonate.
8. method according to claim 1 is characterized in that, coating the treatment time is 1～2 hour.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400422C (en) * | 2005-12-29 | 2008-07-09 | 上海耀华纳米科技有限公司 | Plate-like light calcium carbonate and preparation technology thereof |
| CN101531391B (en) * | 2009-04-16 | 2011-05-18 | 芜湖卓越纳米新材料有限公司 | Method for industrially preparing nanometer calcium carbonate for solvent type ink addition agent |
| CN103663527B (en) * | 2012-09-25 | 2016-02-10 | 上海华明高技术（集团）有限公司 | The preparation method of cubic ultra-fine calcium carbonate particle |
| CN103318938A (en) * | 2013-06-25 | 2013-09-25 | 上海应用技术学院 | Method for preparing calcium carbonate special for printing ink |
| CN104085896B (en) | 2014-07-18 | 2015-12-09 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | The preparation method of active calcium silicate |
| CN105820601B (en) * | 2016-04-18 | 2018-09-14 | 安徽省宣城市华纳新材料科技有限公司 | A kind of preparation of top grade Nano calcium carbonate dedicated to printing ink |
| CN106277014B (en) * | 2016-08-04 | 2018-02-16 | 东北大学 | The method that scattered surface modification prepares active superfine calcium carbonate in advance |
| CN106517285B (en) * | 2016-11-21 | 2017-11-14 | 广西华纳新材料科技有限公司 | A kind of preparation method of rod-like nano calcium carbonate |
| CN108821322B (en) * | 2018-07-12 | 2020-12-08 | 广西华纳新材料科技有限公司 | Preparation method of microsphere precipitated calcium carbonate with layered structure |
| CN109111762A (en) * | 2018-10-09 | 2019-01-01 | 河南骏化发展股份有限公司 | A kind of preparation method of ink modified nano calcium carbonate |
| CN109650430B (en) * | 2018-12-20 | 2021-06-15 | 广西华纳新材料科技有限公司 | Method for preparing nano calcium carbonate from limestone with high magnesium content |
| CN112028100A (en) * | 2020-06-18 | 2020-12-04 | 芜湖卓越纳米新材料股份有限公司 | Industrial preparation method of high-dispersity nano calcium carbonate for printing ink |
| CN114212812B (en) * | 2021-11-01 | 2023-11-21 | 山东宇信纳米科技有限公司 | Preparation method of nano calcium carbonate for PVC edge banding |
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