CN117756410A - Flash ink for ceramic ink-jet printing and preparation method and application thereof - Google Patents
Flash ink for ceramic ink-jet printing and preparation method and application thereof Download PDFInfo
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- CN117756410A CN117756410A CN202311626591.9A CN202311626591A CN117756410A CN 117756410 A CN117756410 A CN 117756410A CN 202311626591 A CN202311626591 A CN 202311626591A CN 117756410 A CN117756410 A CN 117756410A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 97
- 238000007641 inkjet printing Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 40
- LXXCECZPOWZKLC-UHFFFAOYSA-N praseodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LXXCECZPOWZKLC-UHFFFAOYSA-N 0.000 claims abstract description 32
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010304 firing Methods 0.000 claims abstract description 20
- 229910052656 albite Inorganic materials 0.000 claims abstract description 16
- 239000010434 nepheline Substances 0.000 claims abstract description 16
- 229910052664 nepheline Inorganic materials 0.000 claims abstract description 16
- 239000010456 wollastonite Substances 0.000 claims abstract description 16
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 16
- 239000010453 quartz Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 239000010459 dolomite Substances 0.000 claims abstract description 13
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 13
- 239000004576 sand Substances 0.000 claims abstract description 13
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 13
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000454 talc Substances 0.000 claims abstract description 12
- 235000012222 talc Nutrition 0.000 claims abstract description 12
- 229910052623 talc Inorganic materials 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004327 boric acid Substances 0.000 claims abstract description 11
- 239000004927 clay Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 35
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 19
- 238000009472 formulation Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000002689 soil Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- CJFLBOQMPJCWLR-UHFFFAOYSA-N bis(6-methylheptyl) hexanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCC(=O)OCCCCCC(C)C CJFLBOQMPJCWLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- UNOGLHIYPXTOGD-UHFFFAOYSA-N isooctyl laurate Chemical compound CCCCCCCCCCCC(=O)OCCCCCC(C)C UNOGLHIYPXTOGD-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 28
- 239000000976 ink Substances 0.000 description 76
- 230000000052 comparative effect Effects 0.000 description 22
- 239000002245 particle Substances 0.000 description 14
- 229910000420 cerium oxide Inorganic materials 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 239000011449 brick Substances 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to the technical field of ceramic ink-jet printing, and provides flash ink for ceramic ink-jet printing, a preparation method and application thereof. The formula of the flash ink is as follows: 40-60 wt% of flash frit powder, 40-60 wt% of ester solvent, 3-8 wt% of dispersing agent and 0-1 wt% of additive; the formula of the flash frit powder comprises: 0 to 19 weight percent of wollastonite, 0 to 13 weight percent of albite, 0 to 32 weight percent of calcined clay, 0 to 5 weight percent of dolomite, 3 to 8 weight percent of zircon sand, 0.5 to 8 weight percent of zinc, 16 to 43 weight percent of quartz, 7.5 to 12 weight percent of cerium nitrate hexahydrate, 0.24 to 0.96 weight percent of praseodymium nitrate hexahydrate, 0.5 to 3.5 weight percent of boric acid, 0 to 2 weight percent of talcum, 0 to 6 weight percent of nepheline, 0 to 12 weight percent of calcined alumina and 0 to 11 weight percent of calcite; wherein, the content of wollastonite and calcite is 0 when the content of albite and nepheline is 0 when the content of calcined clay and calcined alumina is 0 when the content of dolomite and talcum is 0 when the content of albite and nepheline is different; the mass ratio of praseodymium nitrate hexahydrate to cerium nitrate hexahydrate is not more than 0.08. The flash ink can make ceramic tile obtain bright, high-brightness and high-flash and colorful flash effect through ink jet printing and low-temperature quick firing, and the pattern has no ink scattering and uniform color.
Description
Technical Field
The invention relates to the technical field of ceramic ink-jet printing, in particular to flash ink for ceramic ink-jet printing and a preparation method and application thereof.
Background
Today, people have not only met their value in use, but also focused on the aesthetic visual enjoyment of tile products. The ceramic tile products with the flashing effect have unique artistic feelings because of the flashing effect under the light, so the ceramic tile products are widely paid attention to. The ceramic ink-jet printing technology is a digital printing technology for ceramic pattern design, which is developed in the last 70 th century, can realize personalized design and manufacture of ceramic products, and has the characteristics of time saving, material saving, high efficiency and the like, and one of the key technologies is the design of ceramic ink.
Hitherto, most of ceramic products for ceramic inkjet printing with a glittering effect disclosed in the prior art are products to which glittering glazes are applied, and these products not only limit the variety of ceramic tile glazes to be selected, but also limit the application thereof; in addition, in order to achieve a better flashing effect, the amount of flashing substances is usually too much, and the production cost of the product is further raised.
For example, CN105219159A discloses a ceramic flashing glaze ink and a preparation method thereof, wherein the formulation comprises 2 to 10 percent of resin, 30 to 60 percent of organic solvent, 30 to 55 percent of flashing glaze, 5 to 10 percent of hyperdispersant and 0.1 to 3.5 percent of auxiliary agent by weight; the ceramic flashing glaze ink has the advantages of durability, environmental protection, no toxicity and the like. However, the product has lighter flashing effect color and lower brightness, and is not high in product grade; in addition, the process of the invention improves the flash glaze into screen printing ink, screen printing is needed, the screen printing has the defects of low yield and high screen breakage rate, the screen printing needs to press green bricks, the green bricks are easy to be dark and cracked, the high-quality rate of ceramic tile products can be reduced, the pattern of the screen printing is not easy to be replaced, and the product conversion is not flexible.
In addition, in the prior art, some ceramic products with the flashing effect realize the flashing or starlight effect by using the ceramic dry particles, but the products have the defects of expensive materials, poor antifouling property, poor flashing effect and the like.
For example, CN116354603a discloses a ceramic pearlescent dry particle glaze and a preparation method thereof, which is to prepare ceramic flashing dry particles by mixing, melting, ball milling and other processes of aluminum, zinc, barium, titanium, boron, cerium and other compounds, and then to sinter the ceramic flashing dry particles by being matched with a basic glaze with a strong fluxing system, so as to form a ceramic product with pearlescent effect. The ceramic tile products have complex manufacturing steps, the ball milling is required to be controlled finely, and the zirconium beads are used more, so that the manufacturing cost of the ceramic tile products is higher; in addition, the process makes the glaze into the flashing color body, so the whole brick surface has a flashing effect, the effect is single, the pattern of the brick surface cannot be changed, and the characteristic of high brightness and high flashing is difficult to realize.
As another example, CN114380502a discloses a ceramic dry particle with pearl effect, its preparation method and application method, its formulation of flashing product is that calcareous nepheline 25-30%, calcite 7-10%, calcined kaolin 17-40.5%, electric melting zirconia 5-8%, calcined zinc oxide 10-13%, cerium oxide 4-8%, neodymium oxide 0.5-2%, high barium Gao Siya light transparent frit powder 8-12%; the sparkling ceramic product of the invention has stable pearl effect and certain color effect. However, the glossiness, the luster color and the like of the flashing ceramic products are still to be further improved, the firing temperature of the ceramic tile products can be reduced to 1190 ℃ at the minimum, but the firing temperature of the ceramic tile on the market is 1100-1150 ℃ at low temperature, so that the application of the ceramic dry particles is greatly limited; in addition, the adopted flash substances are ceramic dry particles, the preparation process is complex, and the ball milling is required to be controlled finely, so that the preparation cost of the product is higher and is far less flexible than flash ink.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the flash ink for ceramic ink-jet printing, the preparation method and the application thereof, and the flash ink can enable the ceramic tile to obtain the flash effect with bright color, high brightness and high flash and colorful color through ink-jet printing and low-temperature rapid firing in sequence, and the patterns are free from ink scattering and have uniform color.
Based on the above, the invention discloses a flash ink for ceramic ink-jet printing, which comprises the following raw materials: 40-60 wt% of flash frit powder, 40-60 wt% of ester solvent, 3-8 wt% of dispersing agent and 0-1 wt% of additive;
the raw material formula of the flash frit powder is as follows: 0 to 19 weight percent of wollastonite, 0 to 13 weight percent of albite, 0 to 32 weight percent of calcined clay, 0 to 5 weight percent of dolomite, 3 to 8 weight percent of zircon sand, 0.5 to 8 weight percent of zinc, 16 to 43 weight percent of quartz, 7.5 to 12 weight percent of cerium nitrate hexahydrate, 0.24 to 0.96 weight percent of praseodymium nitrate hexahydrate, 0.5 to 3.5 weight percent of boric acid, 0 to 2 weight percent of talcum, 0 to 6 weight percent of nepheline, 0 to 12 weight percent of calcined alumina and 0 to 11 weight percent of calcite;
in the flash frit powder, the content of wollastonite and calcite is 0 when the content of albite and nepheline is 0 when the content of calcined clay and calcined alumina is 0 when the content of dolomite and talcum is 0 when the content of albite and nepheline is different; the mass ratio of the praseodymium nitrate hexahydrate to the cerium nitrate hexahydrate is less than or equal to 0.08.
Preferably, if wollastonite or sintered soil is added into the flash frit powder, the quartz content is 16-28 wt%; if wollastonite or calcined clay is not added, the content of quartz is 40 to 43wt%.
Preferably, the mass ratio of the praseodymium nitrate hexahydrate to the cerium nitrate hexahydrate is 0.04-0.06.
Further preferably, the zircon sand comprises: up to 33wt% SiO 2 0 to 1wt% of Al 2 O 3 At least 65wt% ZrO 2 ；
The purity of the cerium nitrate hexahydrate is at least 99.5 percent by weight;
the praseodymium nitrate hexahydrate has a purity of at least 99.5 percent by weight.
Preferably, the wollastonite comprises: 58 to 60wt% of SiO 2 34-36 wt% of CaO; the calcite comprises: 54 to 57 weight percent CaO;
the albite comprises: 72 to 74 weight percent of SiO 2 15 to 17 weight percent of Al 2 O 3 8 to 10.5 weight percent of Na 2 O,0 to 1wt% of K 2 O; the nepheline comprises: 40 to 42 weight percent of SiO 2 29 to 31wt% of Al 2 O 3 5 to 6 weight percent of CaO and 11 to 13 weight percent of Na 2 O；
The soil firing comprises: 54 to 56wt% of SiO 2 41 to 43wt% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The calcined alumina comprises: at least 99wt% of Al 2 O 3 ；
The dolomite comprises: 29.5 to 30.5 weight percent of CaO and 21-23 wt% MgO; the talc comprises: 65-66 wt% of SiO 2 0 to 2 weight percent of CaO and 30 to 33 weight percent of MgO.
Preferably, the raw zinc contains at least 99% ZnO; the quartz contains at least 99.5% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The purity of the boric acid is at least 99.5% by weight.
Preferably, the dispersing agent is one or more of Huihong HP 1062, lu Borun Solsperse 13940 and Pick BYKJET-9142;
the additive is one or a mixture of a plurality of binding agent, drier and preservative; wherein the bonding agent is selected from titanate coupling agent or aluminate coupling agent; the drier and the preservative are isopropanol;
the solvent is one or more of diisooctyl adipate, isooctyl laurate, diisooctyl triethylene glycol and D120 solvent oil.
The invention also discloses a preparation method of the flash ink for ceramic ink-jet printing, which comprises the following preparation steps:
(1) Weighing wollastonite, albite, soil, dolomite, zircon sand, raw zinc, quartz, cerium nitrate hexahydrate, praseodymium nitrate hexahydrate, boric acid, talcum, nepheline, calcined alumina and calcite according to a formula, uniformly mixing, adding a proper amount of deionized water to prevent dust from drifting, firing the prepared mixed powder at 1450-1550 ℃ for at least 2 hours, carrying out quenching treatment, and grinding to obtain powder D 50 Not more than 5 mu m, thus obtaining the flashing frit powder;
(2) Fully mixing the flash frit powder with a dispersing agent, an additive and an ester solvent to prepare slurry, and grinding the slurry to D 50 After the ink is=0.2-0.6 mu m, the flash ink for ceramic ink-jet printing is obtained after filtering.
The invention also discloses an application of the flash ink for ceramic ink-jet printing, which is to apply the flash ink to the preparation of ceramic tiles in a ceramic ink-jet printing mode, and the application method comprises the following steps:
and sequentially applying ground glaze and overglaze to the cleaned ceramic blank, printing flashing ink on the overglaze by a ceramic ink-jet printer, and then rapidly firing the ceramic blank with the flashing ink applied at 1050-1150 ℃ for 30-50 min to obtain the ceramic tile.
Wherein, the raw material formula of the base glaze is as follows: 64 to 65wt% of SiO 2 11 to 12 weight percent of Al 2 O 3 2.5 to 3 weight percent of Na 2 O, 2-2.5 wt% of K 2 O, 9.5 to 10 weight percent of CaO,1 to 2 weight percent of MgO and 1 to 3 weight percent of B 2 O 3 1 to 1.5wt% of P 2 O 5 And 4 to 5wt% of TiO 2 ；
The raw material formula of the overglaze is as follows: 54 to 56wt% of SiO 2 14 to 16wt% of Al 2 O 3 3 to 4 weight percent of CaO,2 to 3 weight percent of MgO and 3 to 3.45 weight percent of Na 2 O,3 to 3.45 weight percent of K 2 O,5 to 6 weight percent of ZnO,14 to 15 weight percent of BaO and 0.01 to 0.5 weight percent of B 2 O 3 0.01 to 0.5 weight percent of TiO 2 And 0.01 to 0.5wt% Fe 2 O 3 。
Compared with the prior art, the invention at least comprises the following beneficial effects:
in the flash frit powder used in the flash ink for ceramic ink-jet printing, praseodymium nitrate (such as praseodymium nitrate hexahydrate) is adopted to assist cerium nitrate (cerium nitrate hexahydrate), and the mass ratio of the praseodymium nitrate hexahydrate to the cerium nitrate hexahydrate is controlled to be smaller than or equal to 0.08 so as to form more perfect praseodymium-doped cerium oxide crystal flash particles, so that the cerium oxide crystal defects in the flash frit powder are fewer, compared with the flash particles in a general flash product, the crystallinity of the cerium oxide is more improved, the roughness of the surface is lower, the uniformity is better, and the absorption of incident light is reduced; and then a proper amount of zirconia (from zircon sand) is matched, so that a better effect is shown on specular reflection, high glossiness is shown, and the characteristic of high brightness and high flash is realized; the crystal size fine adjustment can be realized by further matching with elements such as zinc, calcium, magnesium and the like in the raw material formula of the flash frit powder, so that the flash frit powder has good reflection effect on light with specific wavelength; so that the ceramic tile can obtain bright color, high brightness and high flashing and has colorful flashing effect, and the problems of ink scattering and uneven color at the pattern are avoided.
In addition, the flash ink of the invention can be printed on the surface glaze of the ceramic tile through digital design patterns and an ink-jet printer, and the ceramic tile product can be obtained after the flash ink is quickly sintered at the low temperature of 1050-1150 ℃. The pattern of the ceramic product ink-jet has bright color, high brightness and high flashing and has colorful excellent flashing effect, and the product conversion is more flexible; the firing temperature of the ceramic product is lower, the process is simple, and the production cost is lower.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Unless otherwise specified, the powders used in the examples below were as follows:
the zircon sand comprises: siO (SiO) 2 : at most 33wt%, al 2 O 3 ：0～1wt％、ZrO 2 : minimum 65wt%.
The nepheline comprises: siO (SiO) 2 ：40～42wt％、Al 2 O 3 ：29～31wt％、CaO：5～6wt％、Na 2 O：11～13wt％。
Talc comprises: siO (SiO) 2 ：65～66wt％、CaO：0～2wt％、MgO：30～33wt％。
Albite comprises: siO (SiO) 2 ：72～74wt％、Al 2 O 3 ：15～17wt％、Na 2 O：8～10.5wt％、K 2 O：0～1wt％。
Wollastonite contains: siO (SiO) 2 ：58～60wt％、CaO：34～36wt％。
The soil burning comprises: siO (SiO) 2 ：54～56wt％、Al 2 O 3 ：41～43wt％。
Dolomite comprises: caO:29.5 to 30.5 weight percent of MgO:21 to 23 weight percent.
The raw zinc contains at least 99% ZnO.
The quartz contains at least 99.5% SiO 2 。
The purity of cerium nitrate hexahydrate is at least 99.5% by weight.
Praseodymium nitrate hexahydrate has a purity of at least 99.5 percent by weight.
The purity of boric acid is at least 99.5% by weight.
The calcined alumina comprises: al (Al) 2 O 3 : at least 99wt%.
Calcite comprises: caO:54 to 57wt%.
Example 1
The flash ink for ceramic ink-jet printing in this embodiment has the following raw material formulation:
wherein the dispersing agent is Pick BYKJET-9142, the additive is aluminate coupling agent, and the ester solvent is mixture of diisooctyl adipate.
Wherein, the raw materials formula of the flash frit powder is as follows:
the preparation method of the flash ink for ceramic inkjet printing in the embodiment comprises the following preparation steps:
(1) Preparing a flashing frit powder: weighing zircon sand, raw zinc, quartz, cerium nitrate hexahydrate, praseodymium nitrate hexahydrate, boric acid, calcined alumina, calcite, nepheline and talcum according to a formula, uniformly mixing, adding a proper amount of deionized water to prevent dust from drifting, placing the prepared mixed powder into a crucible, firing for 2 hours at 1500 ℃ by a high-temperature furnace, quenching water after firing, and grinding by a vibration mill to obtain powder D 50 And (5) obtaining the flash frit powder.
(2) Manufacturing processPreparing flashing ink: fully mixing the ground flash frit powder with a dispersing agent, an additive and an ester solvent to prepare slurry, fully grinding the slurry to D 50 After=0.2 to 0.6 μm, filtering is performed to obtain the flash ink of the embodiment.
The application method of the flash ink for ceramic ink-jet printing in the embodiment comprises the following steps:
preparing a ceramic blank, cleaning, and applying a base glaze for primary flashing ink and an overglaze for primary flashing ink to the ceramic blank; the flash ink prepared in this example was then printed on the overglaze coated ceramic body by a ceramic ink jet printer at an ink jet rate of 10g/m 2 And then the ceramic blank with the flash ink is quickly sintered in a roller kiln, wherein the sintering temperature is 1135 ℃ and the sintering time is 50min, so that the ceramic product of the embodiment is obtained.
Wherein, the used ground coat comprises the following raw materials: 64.25wt% SiO 2 11.61wt% of Al 2 O 3 2.72wt% Na 2 O,2.14wt% K 2 O,9.85wt% CaO,1.98wt% MgO,1.40wt% B 2 O 3 1.15wt% of P 2 O 5 4.90wt% TiO 2 。
Wherein, the used overglaze comprises the following raw materials: 54.18wt% SiO 2 14.47wt% of Al 2 O 3 3.08wt% CaO,2.12wt% MgO,3.09wt% Na 2 O,3.04wt% K 2 O,5.00wt% ZnO,14.98wt% BaO,0.01wt% B 2 O 3 0.01wt% TiO 2 0.02wt% Fe 2 O 3 。
Example 2
The flash ink for ceramic ink-jet printing in this embodiment has the following raw material formulation:
among them, specific choices of the ester solvent, dispersant and additive are described in example 1.
Wherein, the raw materials formula of the flash frit powder is as follows:
the preparation method of the flash ink for ceramic inkjet printing in the embodiment comprises the following preparation steps:
(1) Preparing a flashing frit powder: weighing albite, wollastonite, sintered soil, dolomite, zircon sand, raw zinc, quartz, cerium nitrate hexahydrate, praseodymium nitrate hexahydrate and boric acid according to a formula, uniformly mixing, adding a proper amount of deionized water to prevent dust from drifting, placing the prepared mixed powder into a crucible, firing for 2 hours at 1450 ℃ through a high-temperature furnace, quenching water after firing, and grinding through a vibration mill to obtain powder D 50 And (5) obtaining the flash frit powder.
(2) Preparing flashing ink: fully mixing the ground flash frit powder with a dispersing agent, an additive and an ester solvent to prepare slurry, fully grinding the slurry to D 50 After=0.2 to 0.6 μm, filtering is performed to obtain the flash ink of the embodiment.
The application method of the flash ink for ceramic inkjet printing in this embodiment is specifically referred to in embodiment 1, and is different from embodiment 1 in that:
the firing temperature of the ceramic body to which the flash ink was applied was 1100 ℃ in a roller kiln for 50 minutes to prepare the ceramic product of this example.
Example 3
The flash ink for ceramic ink-jet printing in this embodiment has the following raw material formulation:
among them, specific choices of the ester solvent, dispersant and additive are described in example 1.
Wherein, the raw materials formula of the flash frit powder is as follows:
the preparation method of the flash ink for ceramic inkjet printing in the embodiment comprises the following preparation steps:
(1) Preparing a flashing frit powder: weighing albite, sintered soil, dolomite, zircon sand, raw zinc, quartz, cerium nitrate hexahydrate, praseodymium nitrate hexahydrate, boric acid and calcite according to a formula, uniformly mixing, adding a proper amount of deionized water to prevent dust from drifting, placing the prepared mixed powder into a crucible, firing for 2 hours at 1550 ℃ through a high-temperature furnace, quenching water after firing, and grinding through a vibration mill to obtain powder D 50 And (5) obtaining the flash frit powder.
(2) Preparing flashing ink: fully mixing the ground flash frit powder with a dispersing agent, an additive and an ester solvent to prepare slurry, fully grinding the slurry to D 50 After=0.2 to 0.6 μm, filtering is performed to obtain the flash ink of the embodiment.
The application method of the flash ink for ceramic inkjet printing in this embodiment is specifically referred to in embodiment 1, and is different from embodiment 1 in that:
the firing temperature of the ceramic body to which the flash ink was applied was 1120 c in a roller kiln for 50 minutes to prepare the ceramic product of this example.
Example 4
The flash ink for ceramic ink-jet printing in this embodiment has the following raw material formulation:
among them, specific choices of the ester solvent, dispersant and additive are described in example 1.
Wherein, the raw materials formula of the flash frit powder is as follows:
the preparation method and the application method of the flash ink for ceramic inkjet printing in this embodiment are specifically referred to embodiment 2, and the difference from embodiment 2 is that:
the firing temperature of the ceramic body to which the flash ink was applied was 1130 deg.c in a roller kiln for 50 minutes to obtain a ceramic product of this example.
Comparative example 1
A ceramic inkjet printing glitter ink according to this comparative example, and a method for producing and using the same, refer to example 1, which differs from example 1 in that:
the raw material formulation of the flash ink of the comparative example was obtained by replacing 9.52wt% of cerium nitrate hexahydrate and 0.48wt% of praseodymium nitrate hexahydrate in the raw material formulation of the flash ink of example 1 with 10wt% of cerium oxide, and the remaining raw materials and contents were unchanged.
Comparative example 2
A ceramic inkjet printing glitter ink according to this comparative example, and a method for producing and using the same, refer to example 2, which differs from example 2 in that:
the raw material formulation of the flash ink of the comparative example was obtained by replacing 9.52wt% of cerium nitrate hexahydrate and 0.48wt% of praseodymium nitrate hexahydrate in the raw material formulation of the flash ink of example 2 with 10wt% of cerium oxide, and the remaining raw materials and contents were unchanged.
Comparative example 3
A ceramic inkjet printing glitter ink according to this comparative example, and a method for producing and using the same, refer to example 3, which differs from example 3 in that:
the raw material formulation of the flash ink of the comparative example was obtained by replacing 9.06wt% of cerium nitrate hexahydrate and 0.45wt% of praseodymium nitrate hexahydrate in the raw material formulation of the flash ink of example 3 with 9.51wt% of cerium oxide, and the remaining raw materials and contents were unchanged.
Comparative example 4
A ceramic inkjet printing glitter ink according to this comparative example, and a method for producing and using the same, refer to example 4, which differs from example 4 in that:
the raw material formulation of the flash ink of the comparative example was obtained by replacing 10.46wt% of cerium nitrate hexahydrate and 0.53wt% of praseodymium nitrate hexahydrate in the raw material formulation of the flash ink of example 4 with 10.99wt% of cerium oxide, and the remaining raw materials and contents were unchanged.
Comparative example 5
A ceramic inkjet printing glitter ink according to this comparative example, and a method for producing and using the same, refer to example 3, which differs from example 3 in that:
the raw material formulation of the flash ink of the comparative example was obtained by replacing 9.06wt% of cerium nitrate hexahydrate and 0.45wt% of praseodymium nitrate hexahydrate (the mass ratio of praseodymium nitrate hexahydrate to cerium nitrate hexahydrate is 0.05) in the raw material formulation of the flash ink of example 3 with 7.925wt% of cerium nitrate hexahydrate and 1.585wt% of praseodymium nitrate hexahydrate (the mass ratio of praseodymium nitrate hexahydrate to cerium nitrate hexahydrate is 0.2); that is, the mass ratio of praseodymium nitrate hexahydrate to cerium nitrate hexahydrate in this comparative example was different from that in example 1, and the sum of the masses of praseodymium nitrate hexahydrate and cerium nitrate hexahydrate in this comparative example was still kept consistent with that in example 1, and the remaining raw materials and contents were unchanged.
Performance testing
The inks prepared in examples 1 to 4 and comparative examples 1 to 5 and the commercially available flash inks were respectively subjected to performance tests, and the test results are shown in table 1 below:
TABLE 1
As can be seen from table 1:
the gloss of the examples 1-4 sparkling ink samples was maintained at a high level, exhibiting excellent sparkling effect; moreover, the inks of the flash ink samples of examples 1 to 4 were relatively concentrated and dense, were not blooming, and were relatively uniform in color; in addition, the examples 1 to 4 were found to have a vivid gloss color, a higher brightness, and a more decorative effect, as compared with the reference commercial glitter ink samples.
In contrast, the glitter materials of the glitter ink samples of comparative examples 1 to 4, which correspond to examples 1 to 4, achieved the glitter effect mainly by directly adding zirconia (derived from zircon sand) and ceria, and the glitter particles of the glitter ink samples of comparative examples 1 to 4 were relatively general in crystallization property, exhibited a macroscopically weaker specular reflection effect than that of the corresponding examples 1 to 4, were weaker in glossiness, and had a slightly uneven color, as well as scattered ink.
Therefore, according to the flash ink sample, the flash frit powder is added with cerium nitrate (such as cerium nitrate hexahydrate) and praseodymium nitrate (such as praseodymium nitrate hexahydrate), so that more perfect praseodymium-doped cerium oxide crystal flash particles are formed, and the crystal flash particles are further matched with zirconium oxide, so that better effects are shown on specular reflection, high glossiness is shown, the characteristic of high brightness and high flash is realized, and the crystal size fine adjustment can be realized by matching with elements such as zinc, calcium, magnesium and the like in the raw material formula of the flash frit powder, so that the crystal size fine adjustment has good reflection effect on light with specific wavelength, further clear color and colorful flash effect are obtained, and the problems of ink scattering and uneven color are avoided.
In addition, as shown in comparative examples 3 and 5, it was found that the gloss effect and gloss color exhibited by the flash ink samples of the present invention were significantly impaired when the mass ratio of praseodymium nitrate hexahydrate to cerium nitrate hexahydrate was large (exceeding 0.08 as in comparative example 5). This means that in the process of adding praseodymium nitrate hexahydrate and cerium nitrate hexahydrate to melt and form praseodymium-doped cerium oxide crystal flash particles, excessive amounts of added praseodymium nitrate hexahydrate may cause larger lattice distortion of the crystal formation and form a second phase praseodymium oxide phase, which in turn greatly affects the size of the bright crystal face of the original praseodymium-doped cerium oxide crystal flash particles, thereby causing the glossiness of the flash ink sample to be weakened and the luster color to be light.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiment and all such alterations and modifications as fall within the scope of the embodiments of the invention.
The foregoing has outlined rather broadly the more detailed description of the invention in order that the detailed description of the invention that follows may be better understood, and in order that the present principles and embodiments may be better understood; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. The flash ink for ceramic ink-jet printing is characterized by comprising the following raw materials in percentage by weight: 40-60 wt% of flash frit powder, 40-60 wt% of ester solvent, 3-8 wt% of dispersing agent and 0-1 wt% of additive;
the raw material formula of the flash frit powder is as follows: 0 to 19 weight percent of wollastonite, 0 to 13 weight percent of albite, 0 to 32 weight percent of calcined clay, 0 to 5 weight percent of dolomite, 3 to 8 weight percent of zircon sand, 0.5 to 8 weight percent of zinc, 16 to 43 weight percent of quartz, 7.5 to 12 weight percent of cerium nitrate hexahydrate, 0.24 to 0.96 weight percent of praseodymium nitrate hexahydrate, 0.5 to 3.5 weight percent of boric acid, 0 to 2 weight percent of talcum, 0 to 6 weight percent of nepheline, 0 to 12 weight percent of calcined alumina and 0 to 11 weight percent of calcite;
in the flash frit powder, the content of wollastonite and calcite is 0 when the content of albite and nepheline is 0 when the content of calcined clay and calcined alumina is 0 when the content of dolomite and talcum is 0 when the content of albite and nepheline is different; the mass ratio of the praseodymium nitrate hexahydrate to the cerium nitrate hexahydrate is less than or equal to 0.08.
2. The flashing ink for ceramic inkjet printing according to claim 1 wherein the content of quartz is 16 to 28wt% when the wollastonite or the calcined clay is added to the flashing frit powder; if wollastonite or calcined clay is not added, the content of quartz is 40 to 43wt%.
3. The flashing ink for ceramic inkjet printing according to claim 1, wherein the mass ratio of praseodymium nitrate hexahydrate to cerium nitrate hexahydrate is 0.04 to 0.06.
4. A flashing ink for ceramic inkjet printing according to claim 1 or 3 wherein the zircon sand comprises: up to 33wt% SiO 2 0 to 1wt% of Al 2 O 3 At least 65wt% ZrO 2 ；
The purity of the cerium nitrate hexahydrate is at least 99.5 percent by weight;
the praseodymium nitrate hexahydrate has a purity of at least 99.5 percent by weight.
5. The flashing ink for ceramic inkjet printing according to claim 1 wherein the wollastonite comprises: 58 to 60wt% of SiO 2 34-36 wt% of CaO; the calcite comprises: 54 to 57 weight percent CaO;
the albite comprises: 72 to 74 weight percent of SiO 2 15 to 17 weight percent of Al 2 O 3 8 to 10.5 weight percent of Na 2 O,0 to 1wt% of K 2 O; the nepheline comprises: 40 to 42 weight percent of SiO 2 29 to 31wt% of Al 2 O 3 5 to 6 weight percent of CaO and 11 to 13 weight percent of Na 2 O；
The soil firing comprises: 54 to 56wt% of SiO 2 41 to 43wt% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The calcined alumina comprises: at least 99wt% of Al 2 O 3 ；
The dolomite comprises: 29.5 to 30.5 weight percent of CaO and 21 to 23 weight percent of MgO; the talc comprises: 65-66 wt% of SiO 2 0 to 2 weight percent of CaO and 30 to 33 weight percent of MgO.
6. A flash ink for ceramic inkjet printing according to claim 1 wherein the raw zinc contains at least 99% ZnO; the quartz contains at least 99.5% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The purity of the boric acid is at least 99.5% by weight.
7. The flashing ink for ceramic inkjet printing according to claim 1 wherein the dispersant is one or more of huihong HP 1062, lu Borun Solsperse 13940 and pick BYKJET-9142;
the additive is one or a mixture of a plurality of binding agent, drier and preservative;
the solvent is one or more of diisooctyl adipate, isooctyl laurate, diisooctyl triethylene glycol and D120 solvent oil.
8. A method for producing a flash ink for ceramic inkjet printing according to any one of claims 1 to 7, characterized by comprising the following production steps:
(1) Weighing wollastonite, albite, soil, dolomite, zircon sand, raw zinc, quartz, cerium nitrate hexahydrate, praseodymium nitrate hexahydrate, boric acid, talcum, nepheline, calcined alumina and calcite according to a formula, uniformly mixing, adding a proper amount of deionized water to prevent dust from drifting, firing the prepared mixed powder at 1450-1550 ℃ for at least 2 hours, carrying out quenching treatment, and grinding to obtain powder D 50 Not more than 5 mu m, thus obtaining the flashing frit powder;
(2) The flash frit powder is sinteredFully mixing the dispersing agent, the additive and the ester solvent to prepare slurry, and grinding the slurry to D 50 After the ink is=0.2-0.6 mu m, the flash ink for ceramic ink-jet printing is obtained after filtering.
9. Use of a flash ink for ceramic inkjet printing according to any one of claims 1 to 7 wherein the flash ink is applied to the preparation of ceramic tiles by means of ceramic inkjet printing, the method of application comprising:
and sequentially applying ground glaze and overglaze to the cleaned ceramic blank, printing flashing ink on the overglaze by a ceramic ink-jet printer, and then rapidly firing the ceramic blank with the flashing ink applied at 1050-1150 ℃ for 30-50 min to obtain the ceramic tile.
10. The use of the flashing ink for ceramic inkjet printing according to claim 9, wherein the raw material formulation of the primer is: 64 to 65wt% of SiO 2 11 to 12 weight percent of Al 2 O 3 2.5 to 3 weight percent of Na 2 O, 2-2.5 wt% of K 2 O, 9.5 to 10 weight percent of CaO,1 to 2 weight percent of MgO and 1 to 3 weight percent of B 2 O 3 1 to 1.5wt% of P 2 O 5 And 4 to 5wt% of TiO 2 ；
The raw material formula of the overglaze is as follows: 54 to 56wt% of SiO 2 14 to 16wt% of Al 2 O 3 3 to 4 weight percent of CaO,2 to 3 weight percent of MgO and 3 to 3.45 weight percent of Na 2 O,3 to 3.45 weight percent of K 2 O,5 to 6 weight percent of ZnO,14 to 15 weight percent of BaO and 0.01 to 0.5 weight percent of B 2 O 3 0.01 to 0.5 weight percent of TiO 2 And 0.01 to 0.5wt% Fe 2 O 3 。
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