Ceramic ink-jet 3D printing supporting ink, preparation method thereof and ceramic ink-jet 3D supporting printing method

Abstract

The invention provides ceramic ink-jet 3D printing supporting ink, a preparation method of the ceramic ink-jet 3D printing supporting ink and a ceramic ink-jet 3D supporting printing method, and relates to the technical field of 3D printing. The ceramic ink-jet 3D printing supporting ink provided by the invention comprises the following preparation raw materials in parts by mass: 10-50 parts of solid particles, 40-80 parts of a solvent, 0-9 parts of a dispersing agent and 0-2 parts of a binder, and the mass parts of the dispersing agent and the binder are not 0. The supporting ink provided by the invention is relatively low in cohesiveness and easy to remove after ceramic ink-jet 3D printing is completed, and the integrity of a sample after removal is ensured; in addition, the supporting ink and the solid ink have good matching performance. According to the ceramic ink-jet 3D supporting printing method, the supporting ink and the entity ink are matched to print the mixed supporting structure, the problem that in the ceramic ink-jet 3D printing process, due to supporting cracking, a green body is damaged is solved, and it is guaranteed that printing is conducted smoothly.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing, and in particular to a ceramic inkjet 3D printing support ink and a preparation method thereof, and a ceramic inkjet 3D support printing method. Background Art

[0002] The direct inkjet 3D printing process of ceramics is generally to print the printing ink onto a heated substrate. After the ink dries (the solvent evaporates), the solid phase particles aggregate and solidify to form a green body. Ceramic inkjet 3D printing generally requires at least two printing inks, one support ink and the other solid ink. The support ink forms a single support layer between the entity and the substrate. After printing is completed, the support is removed, leaving the solid green body, and then the solid green body is sintered to obtain the desired entity.

[0003] Inkjet 3D printing is a layer-by-layer stacking process, which requires that the support will not separate from the substrate during the entire printing period. At the same time, the support must be easily removed after printing is completed. In addition, the support must not be damaged after being scraped by a scraper, which brings many difficulties to the preparation of the support ink. At present, the domestic direct inkjet 3D printing of ceramics is still in its initial stage, and there is relatively little research on support ink. In particular, when only support ink is used as support, the printing is carried out at high temperature, the solvent evaporates, and the capillary stress causes the particles to approach each other, while the bonding strength between the support and the substrate is not high. Long-term printing leads to stress accumulation, and the generated stress may exceed the bonding strength between the support and the substrate; in addition, after the substrate is cooled to room temperature after printing, the support and the entity shrink to a certain extent during the cooling process, and the shrinkage is inconsistent; these may cause the support to crack or even detach from the substrate, and the stress of the support cracking may be transmitted to the entity above, thereby causing cracks in the entity and the support to detach from the substrate, directly leading to the termination of printing. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a ceramic inkjet 3D printing support ink and a preparation method thereof and a ceramic inkjet 3D support printing method. The ceramic inkjet 3D printing support ink provided by the present invention is used in conjunction with solid ink for printing, which can solve the problem of green body being destroyed due to support cracking.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a ceramic inkjet 3D printing support ink, comprising the following raw materials in parts by weight:

[0007] 10 to 50 parts of solid particles, 40 to 80 parts of solvent, 0 to 9 parts of dispersant, and 0 to 2 parts of binder, wherein the mass fractions of the dispersant and binder are not 0; the solid particles are one or more of sodium phenolate, glucose, gelatin, starch, inorganic carbon, bicarbonate, carbonate, chloride and sulfate;

[0008] The viscosity of the ceramic inkjet 3D printing support ink is 10-25 mPas, and the surface tension is 26-36 mN / m.

[0009] Preferably, the ceramic inkjet 3D printing support ink comprises the following raw materials in parts by weight:

[0010] 25-40 parts of solid particles, 55-70 parts of solvent, 1-3 parts of dispersant, and 0.4-2 parts of binder.

[0011] Preferably, the inorganic carbon is one or more of carbon powder, carbon black and graphite powder; the bicarbonate is potassium bicarbonate and / or sodium bicarbonate; the carbonate is one or more of lithium carbonate, potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate and barium carbonate; the chloride is one or more of sodium chloride, potassium chloride, magnesium chloride, calcium chloride and ammonium chloride; the sulfate is one or more of potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate and ammonium sulfate.

[0012] Preferably, the solvent is one or more of water, ethanol, glycerol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, diethylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol butyl ether, ethylene glycol ethyl ether acetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, propylene glycol methyl ether acetate, dibasic acid ester, 1-phenoxy-propanol, N,N-dimethylformamide and N,N-dimethylacetamide.

[0013] Preferably, the dispersant is one or more of BYK105, BYK106, BYK108, BYK109, BYK110, BYK111, BYK163, BYK163F, BYK2163, BYK9130, BYK9132, EFKA4580, EFKA8850, EFKAPX4701, EFKAPX4731, EFKAPX4732, Solsperse 24000, Solsperse 30000, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate and sodium dodecyl sulfate.

[0014] Preferably, the binder is one or more of methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, aldehyde ketone resin, polyacrylate, polyester and polyurethane.

[0015] The present invention provides a method for preparing the ceramic inkjet 3D printing support ink described in the above technical solution, comprising the following steps:

[0016] The solid particles, solvent, dispersant and binder are mixed, and stirred, dispersed and ground in sequence to obtain the ceramic inkjet 3D printing support ink.

[0017] Preferably, the particle size D of the ceramic inkjet 3D printing support ink is 50 97~330nm, D 100 Less than 1μm.

[0018] The present invention also provides a ceramic inkjet 3D support printing method, comprising the following steps:

[0019] Printing solid ink on a heated substrate to form a supporting base layer;

[0020] Solid ink and supporting ink are used simultaneously for printing on the supporting base layer to form a mixed supporting layer, wherein the mixed supporting layer includes solid support formed by the solid ink and pure support formed by the supporting ink, and the solid support and pure support are alternately distributed in the horizontal direction; the supporting ink is the ceramic inkjet 3D printing supporting ink described in the above technical solution or the ceramic inkjet 3D printing supporting ink prepared by the preparation method described in the above technical solution;

[0021] A solid layer is printed on the hybrid support layer.

[0022] Preferably, the spatial ratio of the solid support to the pure support in the mixed support layer is 2:8 to 8:2.

[0023] The present invention provides a ceramic inkjet 3D printing support ink, comprising the following raw materials in mass fractions: 10 to 50 parts of solid particles, 40 to 80 parts of solvents, 0 to 9 parts of dispersants, and 0 to 2 parts of binders, wherein the mass fractions of the dispersants and binders are not 0; the viscosity of the ceramic inkjet 3D printing support ink is 10 to 25 mPas, and the surface tension is 26 to 36 mN / m. The support ink provided by the present invention has low adhesion, is easy to remove after the ceramic inkjet 3D printing is completed, and ensures the integrity of the sample after removal; and the support ink has good matching with the solid ink.

[0024] The present invention provides a ceramic inkjet 3D support printing method, comprising the following steps: using solid ink to print on a heated substrate to form a support base layer; using solid ink and support ink to print on the support base layer at the same time to form a mixed support layer, the mixed support layer includes a solid support formed by the solid ink and a pure support formed by the support ink, and the solid support and the pure support are alternately distributed in the horizontal direction; the support ink is the ceramic inkjet 3D printing support ink described in the above technical solution or the ceramic inkjet 3D printing support ink prepared by the preparation method described in the above technical solution; printing a solid layer on the mixed support layer. The present invention first uses solid ink to print on the heated substrate, and the solid ink has strong bonding performance, which is used as a support base layer to ensure bonding with the substrate; then printing the mixed support layer, when the mixed support layer is printed, while using the support ink to print, introducing a solid ink with strong bonding to print synchronously, which can prevent the support from detaching from the substrate and reduce the cracking caused by inconsistent shrinkage during the cooling process. The present invention solves the problem of green body being destroyed due to support cracking during ceramic inkjet 3D printing by printing a mixed support structure in combination with support ink and solid ink, and ensures smooth printing. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 1 is a structural diagram of a printed part formed by supporting printing in an embodiment of the present invention. Figure 1 (a) is a schematic diagram of the overall structure of the printout. Figure 1 (b) is the cross-sectional view corresponding to (a). Figure 1 In, 1-solid layer, 1-1-solid, 1-2-hybrid support structure, 2-hybrid support layer, 2-1-solid support, 2-2-pure support, 3-support base layer, 4-base plate;

[0026] Figure 2 This is a physical picture of the pure support layer printed with a single support ink in Comparative Example 1;

[0027] Figure 3 This is the surface state of the mixed support layer after being scraped by a scraper in Example 3;

[0028] Figure 4 This is the state of the printed entity (denture) printed according to the method of Example 3 when it is removed from the support. DETAILED DESCRIPTION

[0029] The present invention provides a ceramic inkjet 3D printing support ink, comprising the following raw materials in parts by weight:

[0030] 10 to 50 parts of solid particles, 40 to 80 parts of solvent, 0 to 9 parts of dispersant, and 0 to 2 parts of binder, wherein the mass fractions of the dispersant and binder are not 0; the solid particles are one or more of sodium phenolate, glucose, gelatin, starch, inorganic carbon, bicarbonate, carbonate, chloride and sulfate;

[0031] The viscosity of the ceramic inkjet 3D printing support ink is 10-25 mPas, and the surface tension is 26-36 mN / m.

[0032] In the present invention, unless otherwise specified, the raw materials involved are commercially available products well known in the art.

[0033] In terms of mass fraction, the ceramic inkjet 3D printing support ink provided by the present invention includes 10 to 50 parts of solid particles, which can be 10, 20, 25, 28, 30, 35 or 40 parts, preferably 25 to 40 parts. In the present invention, the solid particles are preferably one or more of sodium phenolate, glucose, gelatin, starch, inorganic carbon, bicarbonate, carbonate, chloride and sulfate; the inorganic carbon is preferably one or more of carbon powder, carbon black and graphite powder; the bicarbonate is preferably potassium bicarbonate and / or sodium bicarbonate; the carbonate is preferably one or more of lithium carbonate, potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate and barium carbonate; the chloride is preferably one or more of sodium chloride, potassium chloride, magnesium chloride, calcium chloride and ammonium chloride; the sulfate is preferably one or more of potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate and ammonium sulfate; in an embodiment of the present invention, the solid particles are more preferably carbon black, calcium chloride or ammonium chloride. In the present invention, the particle size of the solid particles is preferably 10 to 20,000 nm, which is specifically determined by the diameter of the inkjet printing nozzle. In the present invention, the solid particles exist as a support after the solvent evaporates, and the solid particles can be easily removed by melting, sintering, water washing, acid washing, alkali washing, etc. after printing without affecting the integrity of the physical sample.

[0034] In terms of the mass fraction of the solid particles, the ceramic inkjet 3D printing support ink provided by the present invention includes 40 to 80 parts of solvent, which can be 40, 45, 50, 55, 56, 60, 65, 69, 70 or 80 parts, preferably 55 to 70 parts. In the present invention, the solvent is preferably one or more of water, ethanol, glycerol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, diethylene glycol methyl ether acetate, diethylene glycol butyl ether, ethylene glycol ethyl ether acetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, propylene glycol methyl ether acetate, dibasic acid ester, 1-phenoxy-propanol, N,N-dimethylformamide and N,N-dimethylacetamide, more preferably a mixed solvent of ethanol, diethylene glycol methyl ether acetate and glycerol, or tripropylene glycol methyl ether and N,N-dimethylacetamide. The invention discloses a mixed solvent of methylformamide, or a mixed solvent of ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate, wherein the mass ratio of ethanol, diethylene glycol methyl ether acetate and glycerol in the mixed solvent of ethanol, diethylene glycol methyl ether acetate and glycerol is preferably 10:45:14, the mass ratio of tripropylene glycol methyl ether and N,N-dimethylformamide in the mixed solvent of tripropylene glycol methyl ether and N,N-dimethylformamide is preferably 3:8, and the mass ratio of ethylene glycol ethyl ether acetate to propylene glycol methyl ether acetate in the mixed solvent of ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate is preferably 5:9.

[0035] The ceramic inkjet 3D printing support ink provided by the present invention includes 0 to 9 parts of a dispersant, based on the mass fraction of the solid particles, which may be 1, 2, 2.2, 2.3, 3, 4, 5, 6, 7, 8 or 9 parts, preferably 1 to 3 parts. In the present invention, the dispersant is preferably one or more of BYK105, BYK106, BYK108, BYK109, BYK110, BYK111, BYK163, BYK163F, BYK2163, BYK9130, BYK9132, EFKA4580, EFKA8850, EFKAPX4701, EFKAPX4731, EFKAPX4732, Solsperse24000, Solsperse 30000, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate and sodium dodecyl sulfate, more preferably BYK9130, or a mixed dispersant of EFKA4580 and sodium dodecyl sulfonate, or Solsperse The mixed dispersant of Solsperse 30000 and sodium dodecyl sulfate, the mass ratio of EFKA4580 to sodium dodecyl sulfate in the mixed dispersant of EFKA4580 and sodium dodecyl sulfate is preferably 1:4, and the mass ratio of Solsperse 30000 to sodium dodecyl sulfate in the mixed dispersant of Solsperse 30000 and sodium dodecyl sulfate is preferably 1:1.

[0036] In terms of the mass fraction of the solid particles, the ceramic inkjet 3D printing support ink provided by the present invention includes 0 to 2 parts of a binder, which may be 0.2, 0.4, 0.8, 1, 1.5 or 2 parts, preferably 0.4 to 2 parts. In the present invention, the binder is preferably one or more of methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, aldehyde ketone resin, polyacrylate, polyester and polyurethane, more preferably polyurethane, or a mixed binder of ethyl cellulose and polyacrylate, or a mixed binder of polyvinyl alcohol and hydroxyethyl cellulose, the mass ratio of ethyl cellulose to polyacrylate in the mixed binder of ethyl cellulose and polyacrylate is preferably 1:1, and the mass ratio of polyvinyl alcohol to hydroxyethyl cellulose in the mixed binder of polyvinyl alcohol and hydroxyethyl cellulose is preferably 1:1. The present invention adds a small amount of binder and dispersant to ensure that the support ink has a certain bonding strength and is not damaged by a scraper.

[0037] In the present invention, the viscosity of the ceramic inkjet 3D printing support ink (cone and plate viscometer, 60 r / min, 25° C.) is 10 to 25 mPas, preferably 15 to 20 mPas, and the surface tension is preferably 26 to 36 mN / m, more preferably 26 to 33 mN / m.

[0038] The support ink provided by the present invention has low adhesion and is easy to remove after the ceramic inkjet 3D printing is completed, and the integrity of the sample after removal is guaranteed; moreover, the support ink has good matching with the entity ink, which is manifested in that: the support ink and the entity ink are printed at the same time, and the volatility can be as consistent as possible; the entity is printed on the support formed by the support ink, and the entity will not be separated from the support, and the bonding is good; the support formed by the support ink is easy to be removed from around the entity without destroying the integrity of the entity.

[0039] The present invention provides a method for preparing the ceramic inkjet 3D printing support ink described in the above technical solution, comprising the following steps:

[0040] The solid particles, solvent, dispersant and binder are mixed, and stirred, dispersed and ground in sequence to obtain the ceramic inkjet 3D printing support ink.

[0041] In the present invention, the stirring and dispersing is preferably carried out by a high-speed dispersing mixer, and preliminary dispersion is carried out by the stirring and dispersing. In the present invention, the grinding is preferably carried out in a sand mill, and the grinding is preferably carried out with 0.6 mm zirconium oxide balls as grinding balls, and the ball-to-material ratio is preferably 70:30. The rotation speed of the grinding is preferably 300 to 3000 rpm, more preferably 1000 to 2000 rpm, and the time is preferably 30 to 300 min, more preferably 60 to 240 min. After the grinding, the obtained ink is filtered, and the pore size of the filter mesh is preferably 3 μm.

[0042] In the present invention, the particle size D of the ceramic inkjet 3D printing support ink is 50 Preferably 97 to 330 nm, D 100 Preferably it is less than 1 μm.

[0043] The preparation method provided by the invention is simple and has high efficiency.

[0044] The present invention also provides a ceramic inkjet 3D support printing method, comprising the following steps:

[0045] Printing solid ink on a heated substrate to form a supporting base layer;

[0046] Solid ink and supporting ink are used simultaneously for printing on the supporting base layer to form a mixed supporting layer, wherein the mixed supporting layer includes solid support formed by the solid ink and pure support formed by the supporting ink, and the solid support and pure support are alternately distributed in the horizontal direction; the supporting ink is the ceramic inkjet 3D printing supporting ink described in the above technical solution or the ceramic inkjet 3D printing supporting ink prepared by the preparation method described in the above technical solution;

[0047] A solid layer is printed on the hybrid support layer.

[0048] The present invention uses solid ink to print on a heated substrate to form a supporting substrate layer. In the present invention, the solid ink is preferably the solid ink C808 of Israel's X-Jet Company. In the present invention, the heating temperature of the heated substrate is preferably 150-200°C; the thickness of the supporting substrate layer is preferably 500-1000μm. The present invention first uses solid ink to print on a heated substrate. The solid ink has strong bonding properties and can ensure the bonding strength between the support and the substrate as a supporting substrate layer.

[0049] After forming the supporting base layer, the present invention uses both solid ink and supporting ink to print on the supporting base layer to form a mixed supporting layer. In the present invention, the solid ink is the same as the solid ink described in the above technical solution. The present invention has no special requirements for the thickness of the mixed supporting layer, preferably to provide a relatively horizontal printing plane. The present invention designs a solid supporting structure on the supporting base layer, and the solid supporting structures are filled with pure supports formed by supporting ink to form a mixed supporting layer in which solid supports and pure supports are alternately distributed in the horizontal direction. In the present invention, the solid support in the mixed supporting layer and the solid support of the supporting base layer are both printed with the same solid ink, and the solid ink itself has strong adhesion, which ensures the bonding strength between the mixed supporting layer and the supporting base layer; at the same time, the pure support part in the mixed supporting layer also has a certain degree of adhesion, which can also promote the bonding strength with the base layer.

[0050] In the present invention, the spatial ratio of the solid support and the pure support in the mixed support layer is preferably 2:8 to 8:2. The present invention controls the solid support and the pure support in an appropriate ratio, which can ensure the bonding strength and the support does not crack, and at the same time ensure that the support is easy to remove after the printing is completed. Specifically, in high-precision ceramic inkjet 3D printing, the layer thickness is generally less than 10μm, so only 10mm ceramic blanks need to print 1000 layers (excluding the support layer), so the support must remain stable for a long time until the printing is completed. If the ratio is too small, that is, there are more pure supports, the support adhesion and strength are too low, and the printing process is easily destroyed, resulting in the termination of the printing process; if the ratio is too large, that is, there are more solid supports, the support adhesion and strength are too large, and it is difficult to remove in the later stage, and it is difficult to separate from the printed sample, thereby destroying the integrity of the printed sample.

[0051] The support must have good adhesion to the substrate and high bonding strength (requires high viscosity) to prevent the substrate from detaching during printing and causing printing to be stopped; it is also required to be easy to detach from the substrate and the entity after printing is completed, so the support strength cannot be too high (requires low viscosity), and there is a contradiction between the requirements for bonding strength in these two aspects. The present invention uses solid ink to print the entity support layer to solve the problem of combining with the substrate; ink with low adhesion (but must have a certain bonding strength to ensure that it is not damaged after passing through the scraper) is used as a pure support, and a solid ink with strong adhesion is introduced when printing the support to prevent the support from detaching from the substrate, while reducing the cracking caused by inconsistent shrinkage during the cooling process. The support ink described in the present invention has good matching with the entity ink. By matching the support ink with the entity ink, the problem of the green body detaching from the substrate and cracking during the ceramic inkjet 3D printing process is solved, ensuring smooth printing.

[0052] After forming the hybrid support layer, the present invention prints a physical layer on the hybrid support layer. In the present invention, the printing method of the physical layer is preferably: on the hybrid support layer, a physical ink is used to print a physical body, and a hybrid support structure is printed around the physical body according to the above method and proportion, and the hybrid support structure wraps the physical body. In the present invention, the physical ink is the same as the physical ink in the above technical solution. In the present invention, the physical body can be printed accordingly according to the actual shape requirements of the green body. The present invention prints a hybrid support structure in proportion around the physical body to support and protect the physical body, and ensure the bonding strength between the physical body and the hybrid support layer to prevent the support from breaking and causing the printing to be terminated.

[0053] After the printing of the physical layer is completed, the obtained print is cooled to room temperature, and then the support is removed. The present invention has no special requirements for the method of removing the support, and methods familiar to those skilled in the art can be used, such as: mechanical scraping; liquid washing (water washing, acid washing or alkali washing); high temperature melting, oxidation or decomposition. In the process of removing the support, avoid damaging the integrity of the printed entity green body. In the present invention, the pure support in the mixed support layer is easy to be removed by the above method without affecting the integrity of the entity sample. The entity support is easy to be damaged and removed during the removal of the pure support due to its small tip size, and finally a solid green body is obtained.

[0054] In order to further illustrate the present invention, the ceramic inkjet 3D printing support ink and its preparation method and the ceramic inkjet 3D support printing method provided by the present invention are described in detail below with reference to examples, but they should not be understood as limiting the scope of protection of the present invention.

[0055] The solid ink used in each embodiment is solid ink C808 produced by Israel's X-Jet company.

[0056] Example 1

[0057] The support ink (carbon support ink) is composed as follows:

[0058] Carbon black 28wt%, ethanol 10wt%, diethylene glycol methyl ether acetate 45wt%, glycerol 14wt%, dispersant BYK9130 2.26wt%, polyurethane (BASF, LR9100) 0.74wt%.

[0059] The support ink was prepared as follows:

[0060] Carbon black, ethanol, glycerol, diethylene glycol methyl ether acetate, dispersant BYK9130 and polyurethane were initially mixed in a mixer and then put into a sand mill for grinding. 0.6 mm zirconium oxide balls were used for grinding, the ball-to-material ratio was 70:30, the speed was 3000 rpm, and the time was 4 hours. After grinding, the support ink was filtered through 3 μm and canned. The ink viscosity was 15 mPas, the surface tension was 33 mN / m, and the particle size was D 50 =97nm, D 100 <1μm.

[0061] The above support ink is used for ceramic inkjet 3D support printing, and the steps are as follows:

[0062] 1) First, a supporting base layer is printed on a heated substrate using solid ink;

[0063] 2) On the supporting base layer, a mixed supporting layer is printed in proportion using solid ink and the above supporting ink, that is, a solid supporting structure is designed on the supporting base layer, and a pure supporting layer formed by supporting ink is used to fill the space between the solid supporting structures, and the ratio of the solid support to the pure supporting space is 2:8;

[0064] 3) Print the entity on the mixed support layer, and print the mixed support around the entity according to the proportion in 2). The structure of the printed part is as follows: Figure 1 As shown in (a), Figure 1 (b) is the cross-sectional view corresponding to (a).

[0065] After printing is completed, the support is removed using a mechanical tool, and then the ceramic green body is sintered at a high temperature, and the remaining support is oxidized and removed.

[0066] Example 2

[0067] The supporting ink (ammonium chloride supporting ink) is composed of 40wt% ammonium chloride, 20wt% ethylene glycol ethyl ether acetate, 36wt% propylene glycol methyl ether acetate, 1wt% dispersant Solsperse 30000, 1wt% sodium dodecyl sulfate, 1wt% polyvinyl alcohol (weight average molecular weight 20,000 to 40,000), and 1wt% hydroxyethyl cellulose.

[0068] The support ink was prepared as follows:

[0069] Ammonium chloride, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, dispersant Solsperse 3000, sodium lauryl sulfate, polyvinyl alcohol and hydroxyethyl cellulose were mixed in a mixer and then ground in a sand mill. A 0.6 mm zirconium oxide ball was used for grinding, the ball-to-material ratio was 70:30, the speed was 1000 rpm, and the time was 2 h. After grinding, the support ink was filtered through 3 μm and canned. The ink viscosity was 20 mPas, the surface tension was 36 mN / m, and the particle size was D 50 =153nm, D100 <1μm.

[0070] The above support ink is used for ceramic inkjet 3D support printing, and the steps are as follows:

[0071] 1) First, a supporting base layer is printed on a heated substrate using solid ink;

[0072] 2) On the supporting base layer, a mixed supporting layer is printed in proportion using solid ink and the above supporting ink, that is, a solid supporting structure is designed on the supporting base layer, and the space between the solid supporting structures is filled with a pure supporting layer formed by supporting ink, and the ratio of the solid support to the pure support space is 5:5;

[0073] 3) Start printing the entity on the mixed support layer, and print the mixed support around the entity in the proportion in 2).

[0074] After printing is complete, the green body is placed in a furnace for sintering, and the supports are removed by pyrolysis.

[0075] Example 3

[0076] The supporting ink (calcium chloride supporting ink) is composed as follows:

[0077] Calcium chloride 40wt%, tripropylene glycol methyl ether 15wt%, N,N-dimethylformamide 39.6wt%, dispersant EFKA45801wt%, sodium dodecyl sulfate 4wt%, ethyl cellulose 0.2wt%, polyacrylate (Dow Chemical B-44) 0.2wt%.

[0078] The support ink was prepared as follows:

[0079] Calcium chloride, tripropylene glycol methyl ether, N,N-dimethylformamide, dispersant EFKA458, sodium dodecyl sulfonate, ethyl cellulose and polyacrylate were mixed in a mixer and then ground in a sand mill. A 0.6 mm zirconium oxide ball was used for grinding, the ball-to-material ratio was 70:30, the speed was 300 rpm, the time was 2 h, and after the initial grinding, the grinding was carried out at 2000 rpm for 1 h. After grinding, the support ink was filtered through 3 μm and canned. The ink viscosity was 18 mPas, the surface tension was 26 mN / m, and the particle size was D 50 =330nm, D 100 <1μm.

[0080] The above support ink is used for ceramic inkjet 3D support printing, and the steps are as follows:

[0081] 1) First, a supporting base layer is printed on a heated substrate using solid ink;

[0082] 2) On the supporting base layer, a mixed supporting layer is printed in proportion using solid ink and the above supporting ink, that is, a solid supporting structure is designed on the supporting base layer, and a pure supporting layer formed by supporting ink is used to fill the space between the solid supporting structures, and the ratio of the solid support to the pure supporting space is 2:8;

[0083] 3) Print the entity on the hybrid support layer, and print the hybrid support around the entity in the proportion in 2).

[0084] After printing is completed, the green body is placed in water for cleaning to remove the support.

[0085] Comparative Example 1

[0086] Step 2) in Example 3 is changed to printing with a single supporting ink, and the rest is consistent with Example 3.

[0087] Figure 2 This is a physical picture of the pure support layer printed with a single support ink in Comparative Example 1. It can be seen that there are cracks on the pure support surface (in the red circle).

[0088] Figure 3 This is the surface state of the mixed support layer of Example 3 after being scraped. It can be seen that it is well bonded to the substrate without cracks.

[0089] Figure 4 This is the state of the printed entity (denture) printed according to the method of Example 3 without support, wherein the grid shape is the solid filling left after the pure support is washed away. It can be seen that the printing effect is good and the printed entity has no defects in appearance.

[0090] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A ceramic inkjet 3D printing support ink, characterized in that: The preparation comprises the following raw materials in parts by weight: 10 to 50 parts of solid particles, 40 to 80 parts of solvent, 0 to 9 parts of dispersant, and 0 to 2 parts of binder, wherein the mass fractions of the dispersant and binder are not 0; the solid particles are one or more of sodium phenolate, glucose, gelatin, starch, inorganic carbon, bicarbonate, carbonate, chloride and sulfate; The viscosity of the ceramic inkjet 3D printing support ink is 10-25 mPas, and the surface tension is 26-36 mN / m.

2. The ceramic inkjet 3D printing support ink according to claim 1, characterized in that: The preparation comprises the following raw materials in parts by weight: 25-40 parts of solid particles, 55-70 parts of solvent, 1-3 parts of dispersant, and 0.4-2 parts of binder.

3. The ceramic inkjet 3D printing support ink according to claim 1 or 2, characterized in that: The inorganic carbon is one or more of carbon powder, carbon black and graphite powder; the bicarbonate is potassium bicarbonate and / or sodium bicarbonate; the carbonate is one or more of lithium carbonate, potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate and barium carbonate; the chloride is one or more of sodium chloride, potassium chloride, magnesium chloride, calcium chloride and ammonium chloride; the sulfate is one or more of potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate and ammonium sulfate.

4. The ceramic inkjet 3D printing support ink according to claim 1 or 2, characterized in that: The solvent is one or more of water, ethanol, glycerol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, diethylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol butyl ether, ethylene glycol ethyl ether acetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, propylene glycol methyl ether acetate, dibasic acid ester, 1-phenoxy-propanol, N,N-dimethylformamide and N,N-dimethylacetamide.

5. The ceramic inkjet 3D printing support ink according to claim 1 or 2, characterized in that: The dispersant is one or more of BYK105, BYK106, BYK108, BYK109, BYK110, BYK111, BYK163, BYK163F, BYK2163, BYK9130, BYK9132, EFKA4580, EFKA8850, EFKA PX4701, EFKAPX4731, EFKAPX4732, Solsperse 24000, Solsperse 30000, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate and sodium dodecyl sulfate.

6. The ceramic inkjet 3D printing support ink according to claim 1 or 2, characterized in that: The binder is one or more of methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, aldehyde ketone resin, polyacrylate, polyester and polyurethane.

7. The method for preparing the ceramic inkjet 3D printing support ink according to any one of claims 1 to 6, characterized in that: The following steps are involved: The solid particles, solvent, dispersant and binder are mixed, and stirred, dispersed and ground in sequence to obtain the ceramic inkjet 3D printing support ink.

8. The preparation method according to claim 7, characterized in that: The particle size D of the ceramic inkjet 3D printing support ink 50 97~330nm, D 100 Less than 1μm.

9. A ceramic inkjet 3D support printing method, characterized in that: The following steps are involved: Printing solid ink on a heated substrate to form a supporting base layer; Solid ink and supporting ink are used simultaneously for printing on the supporting base layer to form a mixed supporting layer, wherein the mixed supporting layer includes solid support formed by the solid ink and pure support formed by the supporting ink, and the solid support and pure support are alternately distributed in the horizontal direction; the supporting ink is the ceramic inkjet 3D printing supporting ink according to any one of claims 1 to 6 or the ceramic inkjet 3D printing supporting ink prepared by the preparation method according to any one of claims 7 to 8; A solid layer is printed on the hybrid support layer.

10. The ceramic inkjet 3D support printing method according to claim 9, characterized in that: The spatial ratio of the solid support and the pure support in the mixed support layer is 2:8 to 8:2.

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