A glass ink for inkjet printing and a preparation method thereof

Abstract

The present invention provides a glass ink for inkjet printing and a preparation method thereof. By weight percentage, the glass ink comprises 10% - 20% of inorganic pigment, 20% - 50% of frit, 2% - 5% of polymer resin, 30% - 60% of solvent, 0.5% - 2% of ZrOCl 2 , 0.1% - 0.5% of surfactant, 0.02% - 1% of auxiliary agent; the frit comprises a melting material and a fluxing agent, and the ratio between the melting material and the fluxing agent is (3:2) - (4:1), and the sintering temperature range after the glass ink is printed on a glass substrate is 680°C - 780°C. The present invention can simultaneously achieve the tempering of glass and the sintering of the ink only through one heating. Meanwhile, the color display effect of the inorganic pigment is ensured, and the problem that the color is dark after the sintering of the glass ink is solved.

Description

Technical Field

[0001] The present invention relates to the field of glass inks, and specifically relates to a glass ink for inkjet printing and a preparation method thereof. Background Art

[0002] Currently, the common processing method in the field of glass decoration is screen printing. However, the screen printing process is complex, requires a large amount of labor input, and causes certain pollution to the environment during the printing process.

[0003] In recent years, a technology has emerged that uses inkjet printing to non-contact print digital patterns in a computer onto the surface of glass through a nozzle. This technology uses a dedicated inkjet printing device to print glass inkjet printing ink that can adhere to the glass surface onto the glass surface, and then sinter the glass at a high temperature to fuse the ink with the surface of the glass and fix it on the glass surface. By using this method, the environmental pollution is small. By using the inkjet printing method, fast printing of delicate patterns can be achieved, which saves labor and greatly improves the printing accuracy.

[0004] When inkjet printing on a glass substrate, due to the smooth surface of the glass, the adhesion requirement for pigments is relatively high. In the prior art, glass powder is added to the glass ink. After printing on the glass surface, the pattern is sintered, so that the glass powder in the ink and the nearby glass surface are partially melted. In this way, a firm bond between the glass and the printed pattern is achieved.

[0005] However, when the existing glass ink is used, a relatively high temperature needs to be applied for sintering treatment to make the pigment firmly adhere to the glass body. However, when applied to low-melting-point glass, a relatively high sintering temperature may cause the glass substrate to melt. If the temperature is lower than this temperature, the frit will not be completely melted, resulting in poor adhesion performance and easy falling off.

[0006] In addition, when sintering the glass ink, the colorant is prone to chemical reaction with the frit at high temperature, resulting in low color saturation of the sintered pattern. Summary of the Invention

[0007] The first object of the present invention is to provide a glass ink for inkjet printing.

[0008] The second object of the present invention is to provide a preparation method of the above-mentioned glass ink for inkjet printing.

[0009] To achieve the above first object, a glass ink for inkjet printing provided by the present invention includes an inorganic pigment, frit, polymer resin, solvent, and additives. The frit includes a molten material and a flux, and the ratio between the molten material and the flux is (3:2) to (4:1). The glass ink further includes a zirconium-containing compound and a surfactant, and the zirconium-containing compound is ZrOCl 2 ; by weight percentage, the glass ink includes 10% - 20% of inorganic pigment, 20% - 50% of frit, 2% - 5% of polymer resin, 30% - 60% of solvent, 0.5% - 2% of ZrOCl 2 , 0.1% - 0.5% of surfactant, and 0.02% - 1% of additives; the sintering temperature range after the glass ink is printed on a glass substrate is 680°C - 780°C.

[0010] A further solution is that the expansion coefficient of the frit is 8.3 - 8.6×10 -6 / °C, and the ratio between the molten material and the flux is (7:3) to (3:1).

[0011] As can be seen from the above solution, ZrOCl 2 is added in the above solution to protect the inorganic pigment in advance. ZrOCl 2 obtains a stable Zr(OH) 4 sol after hydrolysis. Under the action of the surfactant adsorbed on the surface of the inorganic pigment, a large number of Zr(OH) 4 colloidal particles rich in hydroxyl groups wrap around the surface of the inorganic pigment to complete the encapsulation modification of the inorganic pigment. During the toughening and sintering process, the Zr(OH) 4 colloidal particles on the surface of the inorganic pigment dehydrate and polycondense to form a transparent ZrO 2 film with high chemical stability, preventing the frit from reacting chemically with the inorganic pigment, ensuring the color display effect of the inorganic pigment, and solving the problem of the glass ink being dark in color after sintering. Controlling the ratio of the molten material to the flux within the above range ensures that the sintering temperature is between 680°C and 780°C. If too little flux is added, the melting point of the frit will be too high and it cannot be completely sintered at 680°C - 780°C, resulting in the printed pattern not being able to fuse together on the glass surface. If too much flux is added, the glass will have broken networks, which is not conducive to improving the physical and chemical properties of the glass. The toughening temperature of the glass is between 680°C and 720°C, which exactly coincides with the sintering temperature, and the toughening of the glass and the sintering of the ink can be achieved simultaneously through only one heating. The frit with an expansion coefficient within this range will not crack after sintering on the glass substrate.

[0012] A further solution is that the surfactant includes at least one of an anionic surfactant and a non-ionic surfactant; the anionic surfactant includes at least one of sodium alkyl sulfonate, alkyl aryl sulfonate, sodium alkyl sulfate, and secondary alkyl sulfate; the non-ionic surfactant includes at least one of polyalcohol-based non-ionic surfactants, long-chain fatty alcohol polyoxyethylene ether surfactants, and acetylenic diol modified surfactants.

[0013] As can be seen from the above solutions, the above anionic surfactants can ionize a large number of charged ions in an aqueous solution, firmly adsorb on the surface of inorganic pigment particles, and form an adsorption layer; the above non-ionic surfactants can be adsorbed on the surface of inorganic pigment particles directionally to form an adsorption layer. ZrOCl 2 obtains stable Zr(OH) after hydrolysis 4 The sol particles can be adsorbed on the surface of the adsorption layer to form a coating layer, completing the coating modification of the inorganic pigment and preventing the aggregation of the inorganic pigment at the same time.

[0014] A further solution is that the molten material includes SiO 2 、Al 2 O 3 、B 2 O 3 、ZrO 2 、SnO 2 、La 2 O 3 、TiO 2 two or more of them.

[0015] A further solution is that the flux is at least one of alkali metal oxides and alkaline earth metal oxides.

[0016] A further solution is that the flux includes at least one of Li 2 O, Na 2 O, K 2 O, BaO, Bi 2 O 3 、MgO, SrO, ZnO, PbO, NiO, CoO.

[0017] As can be seen from the above solutions, the combined use of the above molten material and flux can significantly reduce the melting point of the molten material and improve the stability of the frit.

[0018] A further solution is that the inorganic pigment includes at least one of titanium white pigment, chromium green pigment, cobalt blue pigment, iron red pigment, titanium nickel yellow pigment, and copper chromium black pigment.

[0019] A further solution is that the polymer resin includes at least one of methacrylic resins, polyamine resins, and polyurethane resins.

[0020] A further solution is that the solvent is at least one of dipropylene glycol methyl ether acetate, butyrolactone, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethylene glycol, propylene glycol, glycerol, isobutanol, and pentylene glycol; the auxiliary agent is a leveling agent and / or an antifoaming agent.

[0021] As can be seen from the above solution, the above resin can be wrapped on the surface of the powder particles, and the dispersion stability of the inorganic powder can be improved by forming steric hindrance. At the same time, the above resin has good compatibility with other components of the ink, enabling the inorganic powder to be stably suspended in the dispersion system for a long time, further ensuring the dispersion stability and long-term usability of the ink.

[0022] A further solution is that the content of ZrOCl 2 is 1% - 1.5%.

[0023] As can be seen from the above solution, if the addition amount of ZrOCl 2 is too much, it will cause the sintering temperature of the glass ink to increase, resulting in insufficient sintering of the ink at the set temperature. The above range can ensure the wrapping effect of ZrOCl 2 while avoiding too high a sintering temperature.

[0024] In order to achieve the above second object, the present invention provides a preparation method of a glass ink for inkjet printing, for preparing a glass ink for inkjet printing according to any one of the above solutions. The preparation method includes the following steps, by weight percentage:

[0025] S1. Mix the molten material and the flux, fire it into a molten liquid at a high temperature of 1100°C - 1200°C, and keep it warm for 90 min - 120 min; put the molten liquid into water for quenching, and then dry it to obtain frit;

[0026] S2. Put 20% - 50% of the frit, 10% - 20% of the inorganic pigment, 0.5% - 2% of ZrOCl 2 , and part of the solvent into a ball mill, and ball mill at a speed of 600 - 800 rpm for 16 - 20 h to obtain a frit slurry;

[0027] S3. Mix 2% - 5% of the polymer resin, the remaining solvent, 0.1% - 0.5% of the surfactant, 0.02% - 1% of the auxiliary agent with the frit slurry, place it in a ball mill and grind at a speed of 300 - 500 rpm for 2 - 3 h, and filter through a filter membrane with a pore size of 1.0 μm to obtain a glass ink for inkjet printing.

[0028] As can be seen from the above solution, adding the solvent in batches helps the grinding process and improves the grinding efficiency. The glass ink prepared by the above method has a moderate particle size and stable performance. It can be printed on glass by inkjet printing, which is more environmentally friendly and efficient; in addition to printing labels, it can also be used in combination with various color inks to print delicate patterns. Detailed implementation mode

[0029] The present invention will be further described below in conjunction with embodiments.

[0030] The glass ink for inkjet printing of the present invention comprises 10% - 20% inorganic pigment, 20% - 50% frit, 2% - 5% polymer resin, 30% - 60% solvent, 0.5% - 2% ZrOCl 2 , 0.1% - 0.5% surfactant, 0.02% - 1% auxiliary agent; wherein the frit comprises a molten material and a flux, and the ratio between the molten material and the flux is (3:2) - (4:1). The expansion coefficient of the frit is 8.3 - 8.6×10 -6 / °C, and the sintering temperature range after the glass ink is printed on the glass substrate is 680°C - 780°C.

[0031] The preparation method of the glass ink for inkjet printing comprises the following steps, by weight percentage:

[0032] S1. Mix the molten material and the flux, sinter into a molten liquid at a high temperature of 1100°C - 1200°C, and keep warm for 90 min - 120 min; put the molten liquid into water for quenching, and then dry to obtain the frit;

[0033] S2. Put 20% - 50% of the frit, 10% - 20% of the inorganic pigment, 0.5% - 2% of ZrOCl 2 , and part of the solvent into a ball mill, and carry out ball milling at a speed of 600 - 800 rpm for 16 - 20 h to obtain a frit slurry;

[0034] S3. Mix 2% - 5% of the polymer resin, the remaining solvent, 0.1% - 0.5% surfactant, 0.02% - 1% auxiliary agent with the frit slurry, place it in a ball mill and grind at a speed of 300 - 500 rpm for 2 - 3 h, and filter through a filter membrane with a pore size of 1.0 μm to obtain the glass ink for inkjet printing.

[0035] For the process equipment or devices not specifically specified in the following embodiments, conventional equipment or devices in the field are adopted. If not specifically specified, the technical means used in the embodiments of the present invention are all conventional means well-known to those skilled in the art.

[0036] The sources of the raw materials used in the following embodiments are as follows:

[0037] ZrOCl 2 It can be purchased from Xilong Chemical Co., Ltd.;

[0038] The polymer resin includes methacrylic resins, and can be selected from at least one of ACRYPET VH001 of Mitsubishi Corporation of Japan and Carboset 3124 of Lubrizol Corporation. @

[0039] The surfactant includes nonionic surfactant and / or anionic surfactant. The nonionic surfactant includes at least one of polyethylene glycol type nonionic surfactants (such as alkylphenol polyoxyethylene ether --- OP type surfactants: OP-7, OP-10, OP-15, etc.), long-chain fatty alcohol polyoxyethylene ether surfactants (such as Peregal series: Peregal O-20, Peregal O-25, Peregal A-10, etc.) or alkynediol modified surfactants (such as Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, PSA-96, PSA-85, FS-620, FS-640, FS-660, etc.). The anionic surfactant is selected from at least one of sodium alkyl sulfonate, alkyl aryl sulfonate, sodium alkyl sulfate or secondary alkyl sulfate.

[0040] The inorganic pigment includes at least one of titanium white pigment, chromium green pigment, cobalt blue pigment, iron red pigment, titanium nickel yellow pigment and copper chromium black pigment. The solvent is at least one of dipropylene glycol methyl ether acetate, butyrolactone, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethylene glycol, propylene glycol, glycerol, isobutanol and pentylene glycol; the auxiliary agent is a leveling agent and / or an antifoaming agent. The molten material includes SiO 2 Al 2 O 3 B 2 O 3 ZrO 2 SnO 2 La 2 O 3 TiO 2 , and two or more of them. The flux includes at least one of Li 2 O, Na 2 O, K 2 O, BaO, Bi 2 O 3 , MgO, SrO, ZnO, PbO, NiO, CoO. All of the above materials can be purchased from the market.

[0041] The frit of the following examples includes a molten material and a flux, wherein the molten material includes 15% - 30% SiO 2 5% - 10% TiO​2 , 10% - 20% SnO 2 , 20% - 40% B 2 O 3 , 5% - 10% La 2 O 3 , 1% - 10% Al 2 O 3 ; The flux includes 10% - 30% ZnO, 20% - 40% K 2 O, 10% - 35% MgO, 8% - 25% Li 2 O.

[0042] The preparation and pattern printing process of tempered glass in the following examples are as follows:

[0043] 1) Slicing: Cut the original glass into the required shape;

[0044] 2) Pretreatment: Perform edge breaking, edge grinding, drilling and other treatments on the glass;

[0045] 3) Printing: Spray the glass ink of the present invention onto the glass by inkjet printing, and decorative patterns, labels, etc. can be printed.

[0046] 4) Tempering: Place the glass in a firing furnace at 680°C - 720°C for firing, and then perform quenching to obtain tempered glass printed with patterns.

[0047] The technical solutions of the present invention will be further described below with specific examples to better understand the present invention.

[0048] Configure multiple groups of molten materials, and each group of molten materials is configured according to the following weight percentages: 23% SiO 2 , 8% TiO 2 , 19% SnO 2 , 36% B 2 O 3 , 8% La 2 O 3 , and 6% Al 2 O 3 .

[0049] Configure multiple groups of fluxes, and each group of fluxes is configured according to the following weight percentages: 38% K 2 O, 15% MgO, 29% ZnO, 18% Li 2 O.

[0050] The inorganic pigments, polymer resin, surfactant, additives, and solvents in the following specific examples and comparative examples have the same composition.

[0051]

[0052] In the formulations of the examples and comparative examples as described in the table, the ratio of the molten material to the flux added in Examples 1 to 10 is between (3:2) and (4:1), and ZrOCl is not added in Examples 1 to 5. 2 , and the addition amount of ZrOCl in Examples 6 to 9 2 is between 0.5% and 2%, and the addition amount of ZrOCl in Example 10 2 is greater than 2%; ZrOCl is not added in Comparative Examples 1 to 3 2 , and no cosolvent is added in Comparative Example 1. The ratio of the molten material to the cosolvent in Comparative Examples 2 and 3 is greater than 4:1. The addition amount of ZrOCl in Comparative Example 4 2 is between 0.5% and 2%, but the ratio of the molten material to the cosolvent is greater than 4:1.

[0053] Using the above ratios, ink is prepared according to the method described herein. The ink is printed onto glass by inkjet printing, and then the glass is tempered and sintered at 680 °C.

[0054] Observe whether there are bubbles or pattern detachment on the pattern on the glass, and how vivid the pattern color is. The inspection results are as follows:

[0055]

[0056] The above results show that when the ratio of the molten material to the flux is between (3:2) and (4:1), the ink prepared can achieve good sintering at 680 °C. The ink can be completely melted and adhered to the glass, and the printed pattern has good adhesion, the pattern is complete without missing parts, and there are no bubbles or protrusions. When the addition ratio of ZrOCl 2 is between 0.5% and 2%, the printed pattern has a relatively high color vividness. Increasing ZrOCl 2 can well maintain the color vividness, but while increasing the amount of ZrOCl 2 , the hardness also increases, and the melting point also increases accordingly, resulting in a worse sintering pattern effect within the sintering temperature range.

[0057] The specific embodiments described in the present invention are only used for a detailed description of the specific implementation process of the glass ink for inkjet printing, rather than a limitation on its implementation process. Any modification and improvement of this method, and the substitution and use of similar or related substances within the scope of the patent, all fall within the protection scope of the present invention patent.

Claims

1. A glass ink for inkjet printing, characterized in that: By weight percentage, the glass ink comprises 10% to 20% of inorganic pigment, 20% to 50% of frit, 2% to 5% of polymer resin, 30% to 60% of solvent, 0.5% to 2% of ZrOCl 2 , 0.1% to 0.5% of surfactant, 0.02% to 1% of auxiliary agent; the frit comprises a molten material and a flux, and the ratio between the molten material and the flux is (3:2) to (4:1); the surfactant comprises at least one of an anionic surfactant and a nonionic surfactant; the anionic surfactant comprises at least one of sodium alkyl sulfonate, alkyl aryl sulfonate, sodium alkyl sulfate, and secondary alkyl sulfate; the nonionic surfactant comprises at least one of a polyglycol-type nonionic surfactant, a long-chain fatty alcohol polyoxyethylene ether surfactant, and an ethynyl alcohol-modified surfactant; The molten material includes SiO 2 , Al 2 O 3 , B 2 O 3 , ZrO 2 , SnO 2 , La 2 O 3 , TiO 2 and at least two of the following; the flux is at least one of an alkali metal oxide and an alkaline earth metal oxide; the polymer resin comprises at least one of a methacrylic resin, a polyamine resin, and a polyurethane resin; the sintering temperature range after the glass ink is printed on a glass substrate is 680°C to 780°C.

2. A glass ink for inkjet printing according to claim 1, characterized in that: The flux includes Li 2 O, Na 2 O, K 2 O, BaO, Bi 2 O 3 , and at least one of MgO, SrO, ZnO, PbO, NiO, and CoO.

3. A glass ink for inkjet printing according to claim 1, characterized in that: the inorganic pigment comprises at least one of titanium white pigment, chromium green pigment, cobalt blue pigment, iron red pigment, titanium nickel yellow pigment, and copper chromium black pigment.

4. A glass ink for inkjet printing according to claim 1, characterized in that: the solvent is at least one of dipropylene glycol methyl ether acetate, butyrolactone, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethylene glycol, propylene glycol, glycerol, isobutanol, and pentylene glycol; the auxiliary agent is a leveling agent and / or an antifoaming agent.

5. A glass ink for inkjet printing according to claim 1, characterized in that: By weight percentage, the content of ZrOCl 2 is 1% to 1.5%.

6. A preparation method of a glass ink for inkjet printing, characterized in that it is used to prepare a glass ink for inkjet printing according to any one of claims 1 to 5; the preparation method comprises the following steps, by weight percentage: S1. Mix the molten material and the flux, sinter into a molten liquid at a high temperature of 1100°C to 1200°C, and keep warm for 90 min to 120 min; put the molten liquid into water for quenching, and then dry to obtain the frit; S2. Put 20% - 50% of the frit, 10% - 20% of the inorganic pigment, 0.5% - 2% of ZrOCl 2 , and a part of the solvent into a ball mill, and ball mill at a speed of 600 - 800 rpm for 16 - 20 h to obtain a frit slurry; S3. Mix 2% to 5% of the polymer resin, the remaining solvent, 0.1% to 0.5% of the surfactant, 0.02% to 1% of the auxiliary agent with the frit slurry, place it in a ball mill and grind at a rotation speed of 300 - 500 rpm for 2 - 3 h, and filter through a filter membrane with a pore diameter of 1.0 μm to obtain the glass ink for inkjet printing.

Images