CN106810943B - Fade-proof high-temperature-resistant water-based black ink - Google Patents
Fade-proof high-temperature-resistant water-based black ink Download PDFInfo
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- CN106810943B CN106810943B CN201710069240.0A CN201710069240A CN106810943B CN 106810943 B CN106810943 B CN 106810943B CN 201710069240 A CN201710069240 A CN 201710069240A CN 106810943 B CN106810943 B CN 106810943B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims abstract description 11
- 238000005562 fading Methods 0.000 claims abstract description 11
- 239000000049 pigment Substances 0.000 claims abstract description 11
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims abstract description 10
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001661 Chitosan Polymers 0.000 claims abstract description 10
- 229920001287 Chondroitin sulfate Polymers 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000129 anionic group Chemical group 0.000 claims abstract description 10
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 10
- 229940059329 chondroitin sulfate Drugs 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000000787 lecithin Substances 0.000 claims abstract description 10
- 229940067606 lecithin Drugs 0.000 claims abstract description 10
- 235000010445 lecithin Nutrition 0.000 claims abstract description 10
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 10
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 10
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 241000276489 Merlangius merlangus Species 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CDQFODAJQFUTJR-UHFFFAOYSA-M [NH4+].[O-]C(=O)C(=O)O[Ti] Chemical compound [NH4+].[O-]C(=O)C(=O)O[Ti] CDQFODAJQFUTJR-UHFFFAOYSA-M 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 229940045110 chitosan Drugs 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- 238000004040 coloring Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000001041 dye based ink Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to anti-fading high-temperature-resistant water-based black ink which comprises the following raw materials: the coating comprises a black pigment, an anionic waterborne polyurethane-acrylate composite emulsion, carboxymethyl chitosan, polyacrylamide, sodium polyacrylate, chondroitin sulfate, lecithin, superfine aluminum silicate, coarse whiting powder, nano tin, nano silicon dioxide and deionized water. The aqueous black ink improves the coloring and color-preserving performance of the ink, has good stability, does not have the phenomenon of precipitation, layering and agglomeration after long-time storage, is smooth and durable in writing, has stable performance, and does not block a pen point. The ink has good high-temperature resistance, can effectively prevent the ink from fading, and prolongs the storage time of the handwriting; the raw materials are nontoxic and harmless, and are safe and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of ink, and relates to anti-fading high-temperature-resistant water-based black ink.
Background
The ink is a liquid containing a pigment or dye, and can be used for writing or drawing. The black ink includes carbon ink and dye ink. The carbon black ink is commonly used at present, has the advantages of difficult fading, water resistance, corrosion resistance and the like, and has the phenomena of unsmooth writing, easy drying and pen blockage due to intermittent writing and the like because the carbon ink takes carbon particles as a coloring raw material, and colloid is used as a solvent for uniformly distributing carbon, so that the viscosity is high, the particles inside are thick, the pen is easy to block, and the like. The solute of the dye black ink is chemical pigment molecules, and the pigment molecules are used as the colorant, so that the dye black ink has strong liquidity, is not easy to block a pen, and does not damage the pen. However, the formula of dye-based ink usually contains some chemical substances harmful to human body, most pigments are not colored firmly enough, and ink marks are easy to be penetrated, discolored and not beneficial to preservation of documents under the conditions of long-term storage or water and slightly high temperature.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the fade-proof high-temperature-resistant water-based black ink which has the advantages of firm coloring, smooth writing, high temperature resistance and the like.
The technical scheme of the invention is as follows:
the anti-fading high-temperature-resistant water-based black ink comprises the following raw materials in parts by weight: 30-50 parts of black pigment, 3-5 parts of anionic waterborne polyurethane-acrylate composite emulsion, 10-15 parts of carboxymethyl chitosan, 3-5 parts of polyacrylamide, 16-22 parts of sodium polyacrylate, 3-5 parts of chondroitin sulfate, 6-8 parts of lecithin, 5-8 parts of superfine aluminum silicate, 3-5 parts of heavy calcium powder, 3-5 parts of nano tin, 15-17 parts of nano silicon dioxide and 75-90 parts of deionized water.
The black pigment is direct black, acid black, vat black and the like.
The superfine aluminum silicate is 3000 meshes.
The coarse whiting powder is 2500 meshes.
The nano silicon dioxide is preferably modified, and the modification method comprises the following steps: nano SiO2Adding the mixture into ethylene glycol according to the mass ratio of 1: 5-8, performing ultrasonic treatment for 20min, and dropwise adding 3-ammoniaHeating and refluxing the propyl triethoxysilane for 20-24 h, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol, drying, dispersing the filter cake into deionized water, dispersing the deionized water to a concentration of 15-20 g/L, dropwise adding 0.2 mol/L of titanium ammonium oxalate under the protection of inert gas until the concentration of the titanium ammonium oxalate in a system is 15-20 mmol/L, dropwise adding 0.05 mol/L of nitric acid solution to adjust the pH to 2-3, stirring, reacting at 30-50 ℃ for 25-30 h, carrying out suction filtration, washing the filter cake with absolute ethyl alcohol and distilled water in sequence, and carrying out vacuum drying.
The preparation method of the fade-proof high-temperature-resistant water-based black ink comprises the following steps: firstly, sequentially adding polyacrylamide, superfine aluminum silicate and nano silicon dioxide into deionized water, stirring, ultrasonically oscillating for 20-25 min, then adding carboxymethyl chitosan, chondroitin sulfate, lecithin, coarse whiting powder and nano tin, uniformly mixing, rapidly stirring for 15min, then dropwise adding an anionic waterborne polyurethane-acrylate composite emulsion under stirring, sending into a ball mill, carrying out ball milling until the granularity of slurry is 950-1000 nm, finally adding a black pigment and sodium polyacrylate, and stirring for 30min at 50-80 ℃, thus obtaining the nano-composite material.
In the formula of the fade-proof high-temperature-resistant water-based black ink, the anionic water-based polyurethane-acrylate composite emulsion is a novel adhesive, has high surface activity, good ecological safety and intermiscibility, and is formed into a film on the surface of a writing after being dried, and good in water resistance, mechanical property, thermal stability, adhesive force, impact strength, hardness and flexibility. The carboxymethyl chitosan and the polyacrylamide have strong water absorption capacity and high water retention capacity, can repeatedly release and absorb water, effectively prevent dehydration and increase the viscosity of the ink. Lecithin, superfine aluminum silicate and nano tin shell increase the waterproof and heat-resistant properties. The nano silicon dioxide, especially the modified nano silicon dioxide, has good dispersion in aqueous solution, can be compounded with ions brought by other components in an ink formula to initiate a polymerization system, and is subjected to surface graft polymerization, so that the stability of the system is improved, and the problems of precipitation, agglomeration and the like of the nano silicon dioxide are solved. The added sodium polyacrylate is a thickening agent with various special properties, has the function of fixing metal ions and can prevent the negative effect of free metal ions. The coarse whiting powder has weather resistance and color retention, and the chondroitin sulfate effectively improves the lubricating property during writing.
Compared with the prior art, the fade-proof high-temperature-resistant water-based black ink has the beneficial effects that: the coloring and color-preserving performance of the ink is improved, the stability is good, the phenomenon of precipitation, layering and agglomeration cannot occur even if the ink is stored for a long time, the writing is smooth and durable, the performance is stable, and the pen point cannot be blocked. The ink has good high-temperature resistance, can effectively prevent the ink from fading, and prolongs the storage time of the handwriting; the raw materials are nontoxic and harmless, and are safe and environment-friendly.
Detailed Description
The invention is further illustrated by the following specific examples, it being understood that the preparation of the examples is illustrative only and is not intended to be limiting; on the premise of the conception of the invention, simple modification of the preparation method of the invention belongs to the protection scope of the invention.
Example 1
The anti-fading high-temperature-resistant water-based black ink comprises the following raw materials in parts by weight: the paint comprises, by weight, 42 parts of reduced direct black DB, 4 parts of anionic waterborne polyurethane-acrylate composite emulsion, 12 parts of carboxymethyl chitosan, 3.5 parts of polyacrylamide, 20 parts of sodium polyacrylate, 4.1 parts of chondroitin sulfate, 5.5 parts of lecithin, 6.5 parts of 3000-mesh ultrafine aluminum silicate, 4.2 parts of 2500-mesh heavy calcium powder, 4 parts of nano tin, 16 parts of nano silicon dioxide and 87 parts of deionized water.
The preparation method of the fade-proof high-temperature-resistant water-based black ink comprises the following steps: firstly, sequentially adding polyacrylamide, superfine aluminum silicate and nano silicon dioxide into deionized water, stirring, ultrasonically oscillating for 25min, then adding carboxymethyl chitosan, chondroitin sulfate, lecithin, heavy calcium powder and nano tin, uniformly mixing, quickly stirring for 15min, then dropwise adding an anionic waterborne polyurethane-acrylate composite emulsion under stirring, sending into a ball mill, carrying out ball milling until the size of slurry is 950-1000 nm, finally adding reduced direct black DB and sodium polyacrylate, and stirring for 30min at 50-80 ℃, thus obtaining the modified nano silicon dioxide.
Example 2
The anti-fading high-temperature-resistant water-based black ink comprises the following raw materials in parts by weight: the modified polyurethane emulsion comprises, by weight, 50 parts of reduced direct black BCN, 3.2 parts of anionic waterborne polyurethane-acrylate composite emulsion, 10 parts of carboxymethyl chitosan, 3 parts of polyacrylamide, 16.4 parts of sodium polyacrylate, 3 parts of chondroitin sulfate, 6.1 parts of lecithin, 5 parts of 3000-mesh ultrafine aluminum silicate, 3 parts of 2500-mesh heavy calcium powder, 3.4 parts of nano tin, 15 parts of nano silicon dioxide and 75 parts of deionized water.
The preparation method is the same as example 1.
Example 3
The anti-fading high-temperature-resistant water-based black ink comprises the following raw materials in parts by weight: acid black 17234 parts, anionic waterborne polyurethane-acrylate composite emulsion 5 parts, carboxymethyl chitosan 14.8 parts, polyacrylamide 5 parts, sodium polyacrylate 22 parts, chondroitin sulfate 5 parts, lecithin 7.3 parts, 3000-mesh superfine aluminum silicate 7.5 parts, 2500-mesh heavy calcium powder 5 parts, nano tin 4 parts, nano silicon dioxide 17 parts and deionized water 90 parts.
The preparation method is the same as example 1.
Example 4
The difference from the embodiment 1 is that the nano-silica is modified nano-silica, and the modification method comprises the following steps: nano SiO2Adding the mixture into ethylene glycol according to a mass ratio of 1:6, carrying out ultrasonic treatment for 20min, dropwise adding 3-aminopropyltriethoxysilane, heating and refluxing for 20h, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol, drying, dispersing the filter cake into deionized water to a dispersion concentration of 18 g/L, dropwise adding 0.2 mol/L of titanium ammonium oxalate under the protection of inert gas until the concentration of the titanium ammonium oxalate in a system is 15-20 mmol/L, dropwise adding 0.05 mol/L of nitric acid solution to adjust the pH value to 2, stirring, reacting at 30-50 ℃ for 25h, carrying out suction filtration, washing the filter cake with absolute ethyl alcohol and distilled water in sequence, and carrying out vacuum drying.
The results of the ink fade test of the inks prepared in examples 1 to 4 and the ink written on plain paper are shown in Table 1.
TABLE 1
The data of a comparison experiment also show that the ink has the characteristics of strong adhesive force, water immersion resistance, sunlight resistance, high temperature resistance, difficult shedding, stable color and the like, has good pseudoplasticity, large viscosity of the ink when the ink is static, small viscosity of the ink under the action of shearing force, smooth writing, uniform and stable line type, and has the advantages of quick curing time (3-5 s), easy drying, difficult fading and good surface gloss.
Claims (4)
1. The anti-fading high-temperature-resistant water-based black ink is characterized by comprising the following raw materials in parts by weight: 30-50 parts of black pigment, 3-5 parts of anionic waterborne polyurethane-acrylate composite emulsion, 10-15 parts of carboxymethyl chitosan, 3-5 parts of polyacrylamide, 16-22 parts of sodium polyacrylate, 3-5 parts of chondroitin sulfate, 6-8 parts of lecithin, 5-8 parts of superfine aluminum silicate, 3-5 parts of heavy calcium powder, 3-5 parts of nano tin, 15-17 parts of nano silicon dioxide and 75-90 parts of deionized water;
the nano silicon dioxide is modified nano silicon dioxide, and the modification method comprises the following steps: nano SiO2Adding the mixture into ethylene glycol according to a mass ratio of 1: 5-8, carrying out ultrasonic treatment for 20min, dropwise adding 3-aminopropyltriethoxysilane, heating and refluxing for 20-24 h, carrying out suction filtration, washing a filter cake with absolute ethyl alcohol, drying, dispersing the filter cake into deionized water, adjusting the pH to 2-3 by dropwise adding 0.05 mol/L nitric acid solution under the protection of inert gas until the concentration of the titanium ammonium oxalate in a system is 15-20 mmol/L, stirring, reacting at 30-50 ℃ for 25-30 h, carrying out suction filtration, washing the filter cake with absolute ethyl alcohol and distilled water in sequence, and carrying out vacuum drying;
the preparation method of the fade-proof high-temperature-resistant water-based black ink comprises the following steps: firstly, sequentially adding polyacrylamide, superfine aluminum silicate and nano silicon dioxide into deionized water, stirring, ultrasonically oscillating for 20-25 min, then adding carboxymethyl chitosan, chondroitin sulfate, lecithin, coarse whiting powder and nano tin, uniformly mixing, rapidly stirring for 15min, then dropwise adding an anionic waterborne polyurethane-acrylate composite emulsion under stirring, sending into a ball mill, carrying out ball milling until the granularity of slurry is 950-1000 nm, finally adding a black pigment and sodium polyacrylate, and stirring for 30min at 50-80 ℃, thus obtaining the nano-composite material.
2. The fade-resistant, high temperature resistant aqueous black ink of claim 1, wherein: the black pigment is direct black, acid black or reduced black.
3. The fade-resistant, high temperature resistant aqueous black ink of claim 1, wherein: the superfine aluminum silicate is 3000 meshes.
4. The fade-resistant, high temperature resistant aqueous black ink of claim 1, wherein: the coarse whiting powder is 2500 meshes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710069240.0A CN106810943B (en) | 2017-02-08 | 2017-02-08 | Fade-proof high-temperature-resistant water-based black ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710069240.0A CN106810943B (en) | 2017-02-08 | 2017-02-08 | Fade-proof high-temperature-resistant water-based black ink |
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| CN106810943B true CN106810943B (en) | 2020-07-10 |
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Effective date of registration: 20211227 Address after: 526000 No. 16, sanrongxia (Zhaoqing Landai beer Gaoli Co., Ltd.) plant area, western suburb, Zhaoqing City, Guangdong Province Patentee after: Guangdong Zhaoqing Hongying Technology Co.,Ltd. Address before: 271000 class 10 of clinical medicine, School of basic medicine, Shandong First Medical University, Tai'an City, Shandong Province Patentee before: Liu Menghan |
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