CN103923519B - Preparation method of aluminum-based silver paste printing ink with high dispersibility - Google Patents
Preparation method of aluminum-based silver paste printing ink with high dispersibility Download PDFInfo
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- CN103923519B CN103923519B CN201410125794.4A CN201410125794A CN103923519B CN 103923519 B CN103923519 B CN 103923519B CN 201410125794 A CN201410125794 A CN 201410125794A CN 103923519 B CN103923519 B CN 103923519B
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- silver paste
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 95
- 238000007639 printing Methods 0.000 title claims abstract description 67
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 65
- 239000004332 silver Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000012153 distilled water Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 239000008096 xylene Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 94
- 239000004411 aluminium Substances 0.000 claims description 93
- 239000007788 liquid Substances 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 45
- 238000010790 dilution Methods 0.000 claims description 34
- 239000012895 dilution Substances 0.000 claims description 34
- 239000002585 base Substances 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 28
- 150000001398 aluminium Chemical class 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000003760 magnetic stirring Methods 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 238000004506 ultrasonic cleaning Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
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- 239000000758 substrate Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of an aluminum-based silver paste printing ink with high dispersibility. The method comprises the following steps: step 1, carrying out magnetic stirring on aluminum powder taken as a raw material and a solvent I, standing and drying in a vacuum suction filtration manner; step 2, blending the pretreated aluminum powder in a solvent II and stirring in a water bath kettle; step 3, raising the temperature of the water bath, respectively adding two prepared solutions into separating funnels and continuously stirring after dripping; step 4, adding a xylene solution, carrying out ultrasonic dispersion in a numerical-controlled ultrasonic cleaning instrument and transferring into the water bath kettle; step 5, raising the temperature of the water bath, sequentially dripping another three prepared solutions into a final reaction system in the step 4, continuously stirring after the dripping, washing, filtering and carrying out vacuum drying so as to obtain final modified aluminum powder; step 6, mixing the final modified aluminum powder, distilled water, an aiding agent and resin and evenly stirring. The silver paste printing ink prepared by utilizing the method is small in granularity, high in glossiness, strong in corrosion resistance and good in wettability.
Description
Technical field
The invention belongs to water-based silver paste printing ink technical field, relate to the preparation method of the aluminium base silver paste printing ink of a kind of polymolecularity.
Background technology
Miscellaneous metal ink has become the important substance basis in human society life, as its important a member, silver paste printing ink is because of its major ingredient---and aluminium powder has the features such as unique metalluster, effect, shielding, reflectivity, opacifying property and floatability, the dark favor by the field such as Plastics Processing Industry and printing packaging.In view of metal activity, easily agglomeration and the color and luster unicity of silver paste printing ink formula Raw aluminium powder, surface treatment is carried out to it, changes its surface properties, strengthen the corrosion resistance nature of aluminium powder, improving it dispersed, enrich its color developing, is the hot issue that current Related Research Domain is paid close attention to.
Aluminium powder process for modifying surface experienced by inorganic passivation, and------the coated a series of transition process of hybrid modification---high molecular polymer protection---organic/inorganic compound addition polymerization compound relates to the kinds of surface modified techniques such as kinds of surface method of modifying and dry process, wet processing, recombining process such as physics applies, chemistry is coated, precipitin reaction, mechanical force and chemical, encapsulated modification, high energy surface modification in low molecule suppression.Modified aluminium powder obtains important application in the industries such as surface finish and bill printing, and especially at solvent based coating and ink area, silver paste printing ink formulated thus commercially occupies very important status especially.
Prior art carries out improving its erosion resistance under surface treatment is mainly to ensure the prerequisite of its glossiness to aluminium powder, have ignored aluminium powder due to self specific surface area is large, surface energy is high and between organic resin nature difference large and cause easily reunite in actual applications, be difficult to the shortcoming of disperse, sticking power is weak in the coating, the silver paste printing ink granularity obtained thus is large, uneven and come off very easily under external force.The appearance of VOC emission standard and the research requirement to " environmentally friendly " coating for metal surfaces in environmental law in addition, greatly limit the application of aluminium powder in multi-functional coating and silver paste printing ink, actual demand and production status is separated.
Summary of the invention
The object of this invention is to provide the preparation method of the aluminium base silver paste printing ink of a kind of polymolecularity, solve that aluminium base silver paste printing ink of the prior art is easily reunited in actual applications, is difficult to disperse, sticking power is weak in the coating problem.
The technical solution adopted in the present invention is, the preparation method of the aluminium base silver paste printing ink of a kind of polymolecularity, implements according to following steps:
Step 1, joins raw material aluminium powder and solvent one in large beaker simultaneously, and at normal temperatures with after magnetic stirrer, leave standstill, then vacuum filtration, vacuum-drying, obtains pretreated aluminium powder;
Step 2, incorporates solvent two by pretreated aluminium powder, and joins together in four-hole boiling flask, this four-hole boiling flask is placed in electric-heated thermostatic water bath and stirs under the protection of rare gas element;
Step 3, by warming-in-water to 40 ~ 50 DEG C, the methyl silicate of preparation dehydrated alcohol dilution, be called A liquid, prepare the catalyzer of dehydrated alcohol dilution, distilled water and silane coupling agent simultaneously, be called B liquid, A liquid and B liquid are added in separating funnel respectively, controlling to drip speed is 1 drop/sec, dropwise adds in four-hole boiling flask, dropwises rear Keep agitation;
Step 4, adds xylene solution in the end reaction system of step 3, to be placed in numerical control supersonic cleaning apparatus after ultrasonic disperse, to proceed in electric-heated thermostatic water bath;
Step 5, is raised to 75 ~ 90 DEG C by bath temperature, the polymerisable monomer of preparation dehydrated alcohol dilution and linking agent, be called C liquid; The initiator of preparation dehydrated alcohol dilution, is called D liquid; The hydrophilic monomer of preparation dehydrated alcohol dilution, be called E liquid, C liquid, D liquid and E liquid is dripped successively in the end reaction system of step 4, it is 1 drop/sec that speed is dripped in strict control, dropwise add in four-hole boiling flask, after dropwising, Keep agitation, product, through washing, filtration, vacuum-drying, obtains final modified aluminium powder;
Step 6, mixes final modified aluminium powder, distilled water, auxiliary agent and the resin mass ratio according to 1:1:1:10-11, is stirred to range estimation aluminium powder and is uniformly dispersed, be i.e. obtained aluminium base silver paste printing ink.
The invention has the beneficial effects as follows, from main raw material(s)---the aluminium powder of the aluminium base silver paste printing ink of preparation, in conjunction with the limitation that aluminium powder uses, adopt the method for modifying being applicable to aluminium powder being carried out to surface treatment and excellent effect, surface modification treatment is carried out to raw material aluminium powder, not only under the prerequisite ensureing aluminium powder glossiness, improve its erosion resistance, and improve consistency and the dispersiveness of aluminium powder in water of itself and resin, make aluminium powder to be applied in the allotment of silver paste printing ink better.Silver paste printing ink granularity prepared by the present invention is little, glossiness is high, strong solidity to corrosion, wettability are good, for the printability promoting silver paste printing ink is laid a good foundation, also advances the development in water color ink market; This aluminium base silver paste printing ink preparation technology is simple, and service platform is easily built, and improves production efficiency, reduces production cost.
Accompanying drawing explanation
Fig. 1 adopts the made silver paste printing ink of raw material aluminium powder to scrape sample comparison diagram;
Fig. 2 is that the made silver paste printing ink of the inventive method embodiment 1 scrapes sample comparison diagram;
Fig. 3 is that the made silver paste printing ink of the inventive method embodiment 2 scrapes sample comparison diagram;
Fig. 4 is that the made silver paste printing ink of the inventive method embodiment 3 scrapes sample comparison diagram;
Fig. 5 is that the made silver paste printing ink of the inventive method embodiment 4 scrapes sample comparison diagram;
Fig. 6 adopts the dispersed schematic diagram of the made silver paste printing ink of raw material aluminium powder;
Fig. 7 is the dispersed schematic diagram of the made silver paste printing ink of the inventive method embodiment 1;
Fig. 8 is the dispersed schematic diagram of the made silver paste printing ink of the inventive method embodiment 2;
Fig. 9 is the dispersed schematic diagram of the made silver paste printing ink of the inventive method embodiment 3;
Figure 10 is the dispersed schematic diagram of the made silver paste printing ink of the inventive method embodiment 4.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The preparation method of the aluminium base silver paste printing ink of polymolecularity of the present invention, implements according to following steps:
Step 1, joins raw material aluminium powder and solvent one in large beaker simultaneously, and after using magnetic stirrer for some time at normal temperatures, leave standstill, then vacuum filtration, vacuum-drying at 50 DEG C of temperature, obtains pretreated aluminium powder;
Raw material aluminium powder specification in this step is 1000 ~ 1300 orders, solvent one selects dehydrated alcohol, distilled water or acetone, (unit is g) to aluminium powder: the ratio of solvent one (unit is ml) is according to 1g:5ml ~ 1g:10ml proportioning, and churning time is 2h ~ 3h, and time of drying is 2h ~ 3h.
Step 2, incorporates solvent two by pretreated aluminium powder, and joins in the four-hole boiling flask that accurate reinforcement electric mixer and reflux condensing tube are housed together, this four-hole boiling flask is placed in electric-heated thermostatic water bath and stirs under the protection of rare gas element;
Solvent two in this step selects dehydrated alcohol or Virahol, and the mass ratio of pretreated aluminium powder and solvent two is 1:10 ~ 1:25, and rare gas element adopts nitrogen, and churning time is 1h ~ 2h.
Step 3, by warming-in-water to 40 ~ 50 DEG C, temperature variation controls at ± 2 DEG C, prepare catalyzer that the methyl silicate (TMOS) (A liquid) of dehydrated alcohol dilution and dehydrated alcohol dilute, distilled water and silane coupling agent (B liquid) respectively, A liquid and B liquid are added in separating funnel respectively, it is 1 drop/sec that speed is dripped in strict control, dropwise adds in four-hole boiling flask, and dropwising rear Keep agitation is 4h ~ 6h;
Dehydrated alcohol in A liquid and B liquid is 10ml ~ 30ml simultaneously, and methyl silicate, catalyzer, silane coupling agent are 2ml ~ 4ml, and distilled water is 5ml ~ 10ml,
Catalyzer selects ammoniacal liquor or quadrol,
Silane coupling agent selects γ-glycidyl ether oxygen propyl trimethoxy silicane (GPTMS), vinyltriethoxysilane (VTES), vinyltrimethoxy silane (VTMS), methyltrimethoxy silane (MTMS), one of Union carbide A-162 (MTES) or vinyltriacetoxy silane (VTAS).
Step 4, adds xylene solution in the end reaction system of step 3, to be placed in numerical control supersonic cleaning apparatus after ultrasonic disperse for some time, to proceed in electric-heated thermostatic water bath;
Wherein the mass concentration of xylene solution is 0.3g/ml ~ 0.5g/ml, and the mass ratio of dimethylbenzene and aluminium powder is 10:1, and the ultrasonic disperse time is 2h ~ 3h.
Step 5, is raised to 75 ~ 90 DEG C by bath temperature, temperature variation controls at ± 2 DEG C, and the polymerisable monomer of preparation dehydrated alcohol dilution and linking agent, be called C liquid; The initiator (first dissolving with a certain amount of METHYLPYRROLIDONE) of preparation dehydrated alcohol dilution, is called D liquid; The hydrophilic monomer of preparation dehydrated alcohol dilution, be called E liquid, C liquid, D liquid and E liquid is dripped successively in the end reaction system of step 4, it is 1 drop/sec that speed is dripped in strict control, dropwise add in four-hole boiling flask, after dropwising, Keep agitation 3h ~ 6h, product, through washing, filtration, 60 DEG C of dry 4h ~ 6h of Temperature Vacuum, obtains final modified aluminium powder;
Polymerisable monomer wherein selects refined styrene, refining Vinylstyrene selected by linking agent, initiator selects Diisopropyl azodicarboxylate or benzoyl peroxide, hydrophilic monomer selects maleic anhydride, the amount of solvent dehydrated alcohol is 10ml ~ 20ml, and the amount of polymerisable monomer is 4g ~ 6g, and the mass ratio of linking agent and polymerisable monomer is 10% ~ 30%, the mass ratio of initiator and polymerisable monomer is 1% ~ 5%, and hydrophilic monomer is 1 ~ 2:1 with polymerisable monomer molar mass ratio;
The monomer used in this step and linking agent need repeatedly to wash to remove stopper with the NaOH solution of 0.1mol/L and distilled water before use, concrete operation step is: join in separating funnel by a certain amount of monomer/linking agent and NaOH solution, wherein both volume ratios are 10:1, with glass stick hand operated mixing 5min ~ 8min, leave standstill 20min ~ 40min to liquid layered, discharge lower floor's alkali lye, repeatable operation 2 ~ 3 times; Then NaOH solution is changed into distilled water, to the monomer obtained/linking agent washing several times, until the pH of lower floor's expel liquid is close to 7.
Step 6, mixes final modified aluminium powder, distilled water, auxiliary agent and the resin mass ratio according to 1:1:1:10-11, is stirred to range estimation aluminium powder and is uniformly dispersed, be i.e. obtained aluminium base silver paste printing ink of the present invention,
Resin selects acrylic resin, one of polyacrylic resin or polyurethane base resin; Selection of auxiliary defoamer (as methyl-silicone oil), sanitas (as BIT), anti-wear agent (as polyethylene wax), dispersion agent (as amino dodecane base sodium chloroacetate), one of drying retardant (as propylene glycol) or pH value stablizer (as triethylamine).
The preparation method of the aluminium base silver paste printing ink of polymolecularity of the present invention, depends on following principle:
1) carry out pre-treatment to raw material aluminium powder: in the technological process of producing aluminium powder, aluminium powder surface can with the organism such as stearic acid, oleic acid, thus to aluminium powder carry out coated before need with solvent wash, to remove the impurity on its surface.
2) surface modification is carried out to pretreated aluminium powder: by a solvent dispersed for pretreated aluminium powder, drip the different presomas that solvent cut is crossed, be hydrolyzed in aluminium powder surface polymerization under the effect of catalyzer, organic solvent is added after reaction for some time, and introduce polymerisable monomer, linking agent and hydrophilic monomer, under the effect of initiator, carry out graft polymerization reaction, after reaction terminates, obtain final modified aluminium powder by dry for product washing.
Embodiment 1
This kind of polymolecularity aluminium base silver paste printing ink preparation method step is as follows:
Step 1, takes 50g raw material aluminium powder (1000 order) and 250ml acetone joins in beaker, after using magnetic stirrer 2h at normal temperatures, leaves standstill 2h.Then vacuum filtration, vacuum-drying 2h at 50 DEG C of temperature, obtains pretreated aluminium powder;
Step 2, adds the pretreated aluminium powder of 2g and 50ml dehydrated alcohol, stirring at normal temperature 1h under nitrogen protection, makes aluminium powder dispersed in four-hole boiling flask;
Step 3, warming-in-water to 40 DEG C, drip the 2ml methyl silicate (A liquid) of 10ml dehydrated alcohol dilution and 5ml distilled water, 2ml ammoniacal liquor, the 2ml γ-glycidyl ether oxygen propyl trimethoxy silicane (B liquid) of 10ml dehydrated alcohol dilution respectively, controlling rate of addition is 1 drop/sec, about 30min dropwises, Keep agitation 5h;
Step 4, adds 50ml xylene solution in the reaction system of step 3, ultrasonic disperse 2h in amount brought forward controlled ultrasonic wave cleaning apparatus under normal temperature;
Step 5, solution after being uniformly dispersed is proceeded in thermostat water bath, be warming up to 75 DEG C, the 4g refined styrene, the 0.4g that drip the dilution of 10ml dehydrated alcohol respectively refine Vinylstyrene (C liquid), the 0.04g Diisopropyl azodicarboxylate (first dissolving with 5mlN-N-methyl-2-2-pyrrolidone N-) (D liquid) of 10ml dehydrated alcohol dilution and the 3.8g maleic anhydride (E liquid) of 10ml dehydrated alcohol dilution, controlling rate of addition is 1 drop/sec, about 30min dropwises, filter after Keep agitation 3h, product absolute ethanol washing 3 times, 60 DEG C of dry 4h, obtain final modified aluminium powder;
Step 6, final modified aluminium powder, distilled water, defoamer (methyl-silicone oil) and acrylic resin are pressed the mass ratio mixing of 1:1:1:10.5, after stirring 20min ~ 30min, range estimation evenly, obtains aluminium base silver paste printing ink, and be sprayed on paper substrate base plate stand-by after 60 DEG C of dry 72h.
Embodiment 2
This kind of polymolecularity aluminium base silver paste printing ink preparation method step is as follows:
Step 1, takes 50g raw material aluminium powder (1300 order) and 500ml acetone joins in beaker, after using magnetic stirrer 3h at normal temperatures, leaves standstill 3h.Then vacuum filtration, vacuum-drying 3h at 50 DEG C of temperature, obtains pretreated aluminium powder;
Step 2, adds the pretreated aluminium powder of 2g and 50ml Virahol, stirring at normal temperature 2h under nitrogen protection, makes aluminium powder dispersed in four-hole boiling flask;
Step 3, intensification water-bath to 50 DEG C, drip the 4ml methyl silicate (A liquid) of 30ml dehydrated alcohol dilution and 10ml distilled water, 4ml ammoniacal liquor, the 4ml γ-glycidyl ether oxygen propyl trimethoxy silicane (B liquid) of 30ml dehydrated alcohol dilution respectively, controlling rate of addition is 1 drop/sec, about 1h dropwises, Keep agitation 4h;
Step 4, adds 50ml xylene solution in the reaction system of step 3, ultrasonic disperse 3h in amount brought forward controlled ultrasonic wave cleaning apparatus under normal temperature;
Step 5, solution after being uniformly dispersed is proceeded in thermostat water bath, be warming up to 90 DEG C, the 6g refined styrene, the 0.6g that drip the dilution of 20ml dehydrated alcohol respectively refine Vinylstyrene (C liquid), the 0.3g Diisopropyl azodicarboxylate (first dissolving with 5mlN-N-methyl-2-2-pyrrolidone N-) (D liquid) of 20ml dehydrated alcohol dilution and the 11.3g maleic anhydride (E liquid) of 20ml dehydrated alcohol dilution, controlling rate of addition is 1 drop/sec, about 1h dropwises, filter after Keep agitation 6h, product absolute ethanol washing 3 times, 60 DEG C of dry 6h, obtain final modified aluminium powder;
Step 6, presses the mass ratio mixing of 1:1:1:10, stirs, obtain aluminium base silver paste printing ink, and be sprayed on paper substrate base plate stand-by after 60 DEG C of dry 72h by final modified aluminium powder, distilled water, pH value stablizer (triethylamine) and polyacrylic resin.
Embodiment 3
This kind of polymolecularity aluminium base silver paste printing ink preparation method step is as follows:
Step 1, takes 50g raw material aluminium powder (1200 order) and 400ml acetone joins in beaker, after using magnetic stirrer 2h at normal temperatures, leaves standstill 2h.Then vacuum filtration, vacuum-drying 3h at 50 DEG C of temperature, obtains pretreated aluminium powder;
Step 2, adds the pretreated aluminium powder of 2g and 40ml dehydrated alcohol, stirring at normal temperature 1h under nitrogen protection, makes aluminium powder dispersed in four-hole boiling flask;
Step 3, intensification water-bath to 45 DEG C, drip the 2ml methyl silicate (A liquid) of 25ml dehydrated alcohol dilution and 5ml distilled water, 3ml ammoniacal liquor, the 3ml vinyltriethoxysilane (B liquid) of 25ml dehydrated alcohol dilution respectively, controlling rate of addition is 1 drop/sec, 1h dropwises, Keep agitation 5h;
Step 4, adds 50ml xylene solution in the end reaction system of step 3, ultrasonic disperse 2h in amount brought forward controlled ultrasonic wave cleaning apparatus under normal temperature;
Step 5, solution after being uniformly dispersed is proceeded in thermostat water bath, be warming up to 80 DEG C, the 5g refined styrene, the 0.5g that drip the dilution of 10ml dehydrated alcohol respectively refine Vinylstyrene (C liquid), the 0.05g benzoyl peroxide (first dissolving with 5mlN-N-methyl-2-2-pyrrolidone N-) (D liquid) of 10ml dehydrated alcohol dilution and the 4.7g maleic anhydride (E liquid) of 10ml dehydrated alcohol dilution, controlling rate of addition is 1 drop/sec, about 30min dropwises, filter after Keep agitation 4h, product absolute ethanol washing 3 times, 60 DEG C of dry 5h, obtain final modified aluminium powder;
Step 6, final modified aluminium powder, distilled water, dispersion agent (amino dodecane base sodium chloroacetate) and polyurethane base resin are pressed the mass ratio mixing of 1:1:1:11, stir, obtain aluminium base silver paste printing ink, and be sprayed on paper substrate base plate stand-by after 60 DEG C of dry 72h.
Embodiment 4
Polymolecularity of the present invention aluminium base silver paste printing ink preparation method step is as follows:
Step 1, takes 50g raw material aluminium powder (1200 order) and 300ml acetone joins in beaker, after using magnetic stirrer 2h at normal temperatures, leaves standstill 2h.Then vacuum filtration, vacuum-drying 2h at 50 DEG C of temperature, obtains pretreated aluminium powder;
Step 2, adds the pretreated aluminium powder of 2g and 30ml Virahol, stirring at normal temperature 1h under nitrogen protection, makes aluminium powder dispersed in four-hole boiling flask;
Step 3, intensification water-bath to 45 DEG C, drip the 2ml methyl silicate (A liquid) of 20ml dehydrated alcohol dilution and 10ml distilled water, 3ml ammoniacal liquor, the 3ml vinyltriacetoxy silane (B liquid) of 20ml dehydrated alcohol dilution respectively, control rate of addition 1 drop/sec, 1h dropwises, Keep agitation 6h;
Step 4, adds 50ml xylene solution in the end reaction system of step 3, ultrasonic disperse 3h in amount brought forward controlled ultrasonic wave cleaning apparatus under normal temperature;
Step 5, solution after being uniformly dispersed is proceeded in thermostat water bath, be warming up to 85 DEG C, the 5g refined styrene, the 0.5g that drip the dilution of 10ml dehydrated alcohol respectively refine Vinylstyrene (C liquid), the 0.1g benzoyl peroxide (first dissolving with 5mlN-N-methyl-2-2-pyrrolidone N-) (D liquid) of 10ml dehydrated alcohol dilution and the 4.7g maleic anhydride (E liquid) of 10ml dehydrated alcohol dilution, controlling rate of addition is 1 drop/sec, about 30min dropwises, filter after Keep agitation 5h, product absolute ethanol washing 3 times, 60 DEG C of dry 6h, obtain final modified aluminium powder;
Step 6, presses the mass ratio mixing of 1:1:1:10, stirs, obtain aluminium base silver paste printing ink, and be sprayed on paper substrate base plate stand-by after 60 DEG C of dry 72h by final modified aluminium powder, distilled water, drying retardant (propylene glycol) and acrylic resin.
Test result to embodiment sample:
1) glossiness detects
Adopt KGZ-1C type vancometer to measure different glossiness of scraping sample, glossiness detected result is as shown in table 1:
Each embodiment glossiness detected result of table 1 contrasts
| Scrape sample title | Glossiness |
| Raw material aluminium powder silver paste printing ink | 74.3 |
| The made silver paste printing ink of the embodiment of the present invention 1 | 61.2 |
| The made silver paste printing ink of the embodiment of the present invention 2 | 62.7 |
| The made silver paste printing ink of the embodiment of the present invention 3 | 64.5 |
| The made silver paste printing ink of the embodiment of the present invention 4 | 63.1 |
As can be seen from glossiness detected result, compared with the made silver paste printing ink of original aluminium powder, though the silver paste printing ink glossiness prepared by the embodiment of the present invention declines to some extent, but substantially maintain the original glossiness of aluminium powder, do not affect the practical application of silver paste printing ink.
2) profile pattern detects
Get the above-mentioned obtained aluminium base silver paste printing ink of 1cm × 1cm size and scrape sample, the surface finish of the different embodiment of ready visual contrast, thus judge the consistency of resin in modified aluminium powder and ink.As Figure 1-Figure 5, wherein Fig. 1 is raw material aluminium powder silver paste printing ink to result, and Fig. 2 is the made silver paste printing ink of embodiment 1, and Fig. 3 is the made silver paste printing ink of embodiment 2, and Fig. 4 is the made silver paste printing ink of embodiment 3, and Fig. 5 is the made silver paste printing ink of embodiment 4.
As can be seen from Figure 1, the made silver paste printing ink granularity of original aluminium powder is large, uneven, and aluminium powder major part is reunited together, has had a strong impact on the printability of silver paste printing ink; As can be seen from Fig. 2, Fig. 4 and Fig. 5, the made silver paste printing ink granularity of the embodiment of the present invention reduces, and homogeneity promotes, and surface ratio is more smooth; In Fig. 3, silver paste printing ink surface ratio is more coarse may be the impact being subject to Different factor in embodiment, but its homogeneity is still good than Fig. 1, therefore the made silver paste printing ink of the present invention can be used in actual print production.
3, dispersed detection
Take the dispersion of 0.5g modified aluminium powder 5ml distilled water, slide surface is dropped in glass pipette, examine under a microscope its dispersiveness in water, draw out the dispersed result of modified aluminium powder as shown in Fig. 6-Figure 10 in conjunction with observations, wherein "×" represents aluminium powder particle, and Fig. 6 is raw material aluminium powder, Fig. 7 is the made modified aluminium powder of embodiment 1, Fig. 8 is the made modified aluminium powder of embodiment 2, and Fig. 9 is the made modified aluminium powder of embodiment 3, and Figure 10 is the made modified aluminium powder of embodiment 4:
As can be seen from Figure 6, original aluminium powder is very easily assembled agglomerating in water, dispersed very poor; According to the dispersiveness signal result of Fig. 7 to Figure 10, compared with original aluminium powder, the made modified aluminium powder dispersiveness of the embodiment of the present invention has lifting greatly, and especially Fig. 9 and the made modified aluminium powder of embodiment 3 are almost without macrobead clustering phenomena in water, meet its application in water-based silver paste printing ink completely.
Claims (3)
1. a preparation method for the aluminium base silver paste printing ink of polymolecularity, is characterized in that, implements according to following steps:
Step 1, joins raw material aluminium powder and solvent one in large beaker simultaneously, and at normal temperatures with after magnetic stirrer, leave standstill, then vacuum filtration, vacuum-drying, obtains pretreated aluminium powder;
Wherein, raw material aluminium powder specification is 1000 ~ 1300 orders,
Solvent one selects dehydrated alcohol, distilled water or acetone,
Aluminium powder: the ratio of solvent one is 1g:5ml ~ 1g:10ml, and churning time is 2h ~ 3h, and time of drying is 2h ~ 3h;
Step 2, incorporates solvent two by pretreated aluminium powder, and joins together in four-hole boiling flask, this four-hole boiling flask is placed in electric-heated thermostatic water bath and stirs under the protection of rare gas element;
Wherein, solvent two selects dehydrated alcohol or Virahol,
The mass ratio of pretreated aluminium powder and solvent two is 1:10 ~ 1:25, and rare gas element adopts nitrogen, and churning time is 1h ~ 2h;
Step 3, by warming-in-water to 40 ~ 50 DEG C, the methyl silicate of preparation dehydrated alcohol dilution, be called A liquid, prepare the catalyzer of dehydrated alcohol dilution, distilled water and silane coupling agent simultaneously, be called B liquid, A liquid and B liquid are added in separating funnel respectively, controlling to drip speed is 1 drop/sec, dropwise adds in four-hole boiling flask, dropwises rear Keep agitation;
Wherein, the dehydrated alcohol in A liquid and B liquid is 10ml ~ 30ml simultaneously, and methyl silicate, catalyzer, silane coupling agent are 2ml ~ 4ml, and distilled water is 5ml ~ 10ml;
Catalyzer selects ammoniacal liquor or quadrol;
Silane coupling agent selects γ-glycidyl ether oxygen propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane, methyltrimethoxy silane, one of Union carbide A-162 or vinyltriacetoxy silane;
Step 4, adds xylene solution in the end reaction system of step 3, to be placed in numerical control supersonic cleaning apparatus after ultrasonic disperse, to proceed in electric-heated thermostatic water bath;
Wherein, the mass concentration of xylene solution is 0.3g/ml ~ 0.5g/ml, and the mass ratio of dimethylbenzene and aluminium powder is 10:1, and the ultrasonic disperse time is 2h ~ 3h;
Step 5, is raised to 75 ~ 90 DEG C by bath temperature, the polymerisable monomer of preparation dehydrated alcohol dilution and linking agent, be called C liquid; The initiator of preparation dehydrated alcohol dilution, is called D liquid; The hydrophilic monomer of preparation dehydrated alcohol dilution, be called E liquid, C liquid, D liquid and E liquid is dripped in the end reaction system of step 4, it is 1 drop/sec that speed is dripped in strict control, dropwise add in four-hole boiling flask, after dropwising, Keep agitation, product, through washing, filtration, vacuum-drying, obtains final modified aluminium powder;
Wherein, polymerisable monomer selects refined styrene,
Refining Vinylstyrene selected by linking agent,
Initiator selects Diisopropyl azodicarboxylate or benzoyl peroxide,
Hydrophilic monomer selects maleic anhydride,
The amount of solvent dehydrated alcohol is 10ml ~ 20ml, the amount of polymerisable monomer is 4g ~ 6g, the mass ratio of linking agent and polymerisable monomer is 10% ~ 30%, and the mass ratio of initiator and polymerisable monomer is 1% ~ 5%, and hydrophilic monomer is 1 ~ 2:1 with polymerisable monomer molar mass ratio;
Step 6, mixes final modified aluminium powder, distilled water, auxiliary agent and the resin mass ratio according to 1:1:1:10-11, is stirred to range estimation aluminium powder and is uniformly dispersed, be i.e. obtained aluminium base silver paste printing ink.
2. the preparation method of the aluminium base silver paste printing ink of polymolecularity according to claim 1, is characterized in that: in described step 5,
Monomer and linking agent need repeatedly to wash to remove stopper with the NaOH solution of 0.1mol/L and distilled water before use, concrete operation step is: join in separating funnel by monomer/linking agent and NaOH solution, wherein both volume ratios are 10:1, with glass stick hand operated mixing 5min ~ 8min, leave standstill 20min ~ 40min to liquid layered, discharge lower floor's alkali lye, repeatable operation 2 ~ 3 times; Then NaOH solution is changed into distilled water, to the monomer obtained/linking agent washing several times, until the pH of lower floor's expel liquid is close to 7.
3. the preparation method of the aluminium base silver paste printing ink of polymolecularity according to claim 1, is characterized in that: in described step 6,
Resin selects acrylic resin, one of polyacrylic resin or polyurethane-based resin;
Selection of auxiliary defoamer, sanitas, anti-wear agent, dispersion agent, one of drying retardant or pH value stablizer.
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| EP1264866A2 (en) * | 2001-06-05 | 2002-12-11 | Toda Kogyo Corporation | Colorant for ink-jet printing ink, ink-jet printing ink, aqueous pigment dispersion containing the colorant, and organic and inorganic composite particles |
| CN1986648A (en) * | 2006-11-24 | 2007-06-27 | 华南理工大学 | Preparing method of coated aluminium powder pigment |
| CN101235226A (en) * | 2008-02-25 | 2008-08-06 | 中南大学 | Method for preparing silicon dioxide coating type water aluminum-silver slurry |
| CN102093761A (en) * | 2010-11-08 | 2011-06-15 | 深圳职业技术学院 | Preparation method of aqueous aluminum silver paste |
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| EP1264866A2 (en) * | 2001-06-05 | 2002-12-11 | Toda Kogyo Corporation | Colorant for ink-jet printing ink, ink-jet printing ink, aqueous pigment dispersion containing the colorant, and organic and inorganic composite particles |
| CN1986648A (en) * | 2006-11-24 | 2007-06-27 | 华南理工大学 | Preparing method of coated aluminium powder pigment |
| CN101235226A (en) * | 2008-02-25 | 2008-08-06 | 中南大学 | Method for preparing silicon dioxide coating type water aluminum-silver slurry |
| CN102093761A (en) * | 2010-11-08 | 2011-06-15 | 深圳职业技术学院 | Preparation method of aqueous aluminum silver paste |
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