Black organic-inorganic hybrid ink, preparation method and application thereof

Abstract

The application discloses black organic-inorganic hybrid ink as well as a preparation method and application thereof, and belongs to the technical field of ink, wherein the black organic-inorganic hybrid ink is prepared from the following raw materials in parts by weight: organic-inorganic hybrid resin 40-50 parts; silicone resin 5-10 parts; dilution film-forming control additive 8-10 parts; mica powder 5-10 parts; black pigment 20-26 parts; filler 1-3 parts; leveling agent 0.5-1.5 parts; anti-settling agent 2-4 parts; defoaming agent 0.2-0.5 parts; wherein the black pigment is prepared from 5-8 parts of carbon black, 8-10 parts of copper-chromium black, 5-8 parts of aluminum dihydrogen phosphate and 1-2 parts of kaolin in a mixed solution of water and ethanol, and is dried after being heated and dispersed. The black organic-inorganic hybrid ink belongs to the category of medium-temperature ink, raw materials are easy to obtain, temperature resistance reaches 500 DEG C, and long-term use can avoid the problems of ink peeling, carbonization, whitening and the like, and is suitable for various substrates and various printing processes.

Description

Technical Field

[0001] This invention relates to the field of ink technology, specifically to a black organic-inorganic hybrid ink, its preparation method, and its application. Background Technology

[0002] Ink is an indispensable material in the printing process. Through printing or inkjet printing techniques, it brings patterns and text to life on substrates, finding wide application in printing, coatings, packaging, and home appliances. Taking home appliances as an example, ink influences both the appearance and design of products, as well as the clarity of labeling and the ease of button operation. The diverse environments in which home appliances are used place higher demands on the weather resistance, abrasion resistance, and chemical corrosion resistance of inks.

[0003] In the specific home appliance glass industry, the inks used in home appliance glass can be roughly divided into low-temperature, medium-temperature, and high-temperature inks based on their heat resistance. Low-temperature inks typically withstand temperatures below 200℃, requiring only surface drying at around 200℃ after screen printing. They offer a wide range of colors and are suitable for various applications. High-temperature inks can withstand temperatures up to 600℃ and do not change color after prolonged baking. Unlike other inks, they contain a large amount of glass powder added during production. After screen printing, they undergo a tempering process at 650-700℃, melting into the softened glass surface and exhibiting high hardness that prevents scratching. Medium-temperature inks have heat resistance between low-temperature and high-temperature inks, withstanding temperatures of 250-350℃. They are most commonly used in the printing process of borosilicate glass for microwave oven inner partitions.

[0004] With the continuous improvement of science and technology and the development of various industries, higher requirements have been placed on the high-temperature resistance and applicability of inks to various substrates. Taking borosilicate glass as an example, due to the heating of the bottom heating wire, the heat resistance has increased from 350℃ to 500℃. However, conventional medium-temperature inks cannot withstand the high temperature of 500℃, and long-term use will lead to a series of problems such as ink peeling, carbonization, and whitening. Therefore, it is urgent to develop new inks to improve their high-temperature resistance and applicability to various substrates.

[0005] Chinese patent document CN104419246A discloses a high-temperature resistant ink and its preparation method. The raw material composition is: 15%–30% organic resin, 3%–25% solvent, 25%–55% modified pigment, 1%–10% filler, 0.1%–5% leveling agent, and 0.1%–5% dispersant. The modified pigment consists of pigment and low-melting-point lead-free glass powder modified with a silane coupling agent, coated on the outside of the pigment. The ink produced by this invention can cure under medium and low temperature conditions, matching the processing temperature of medium-temperature glass inks. However, in practical use, the maximum temperature resistance can only reach 350℃, which cannot meet the requirements for higher temperature resistance.

[0006] Chinese patent document CN117567902A discloses a high-temperature resistant ink, which comprises the following components by weight: 10-30 parts silicone resin, 15-25 parts polyester-modified methylphenyl silicone resin, 2-8 parts mica powder, 3-15 parts titanium dioxide, 5-7 parts octylphenol polyoxyethylene ether, 10-15 parts anhydrous ethanol, 2-6 parts ethylene glycol monostearate, 10-15 parts nano-SiO2, 1.5-4 parts talc, 2-6 parts glass powder, 7-12 parts chitosan, 0.7-2.5 parts adhesion promoter, 1.0-2.0 parts antistatic agent, 5-10 parts matting agent, 0.2-0.4 parts defoamer, 0.5-1.0 parts leveling agent, and 1.5-3 parts high-temperature resistant additives. This ink can ensure high-temperature resistance while possessing good abrasion resistance and adhesion. However, its coefficient of thermal expansion does not match that of high borosilicate glass, limiting its application to inkjet printing technology and making it unsuitable for screen printing. Furthermore, the raw material, polyester-modified methylphenyl silicone resin, undergoes a chemical reaction at high temperatures, affecting the high-temperature resistance of the ink.

[0007] Therefore, there is an urgent need to develop a medium-temperature ink that can withstand temperatures up to 500°C for extended periods, is compatible with high borosilicate glass, and is suitable for a variety of substrates to solve the aforementioned technical problems. Summary of the Invention

[0008] To address the shortcomings of the existing technology, this invention provides a black organic-inorganic hybrid ink, which falls under the category of medium-temperature inks. The raw materials are readily available, and the temperature resistance reaches 500℃. Long-term use can avoid problems such as ink peeling, carbonization, and whitening. It meets the requirements of high borosilicate glass printing processes and is suitable for various substrates (glass, metal, etc.) and various printing processes (inkjet printing, screen printing, etc.).

[0009] The specific technical solution adopted is as follows:

[0010] A black organic-inorganic hybrid ink, made from the following raw materials in parts by weight:

[0011] 40-50 parts of organic-inorganic hybrid resin;

[0012]

[0013] The black pigment is prepared by dissolving 5-8 parts carbon black, 8-10 parts copper chromium black, 5-8 parts aluminum dihydrogen phosphate and 1-2 parts kaolin in a mixed solution of water and ethanol, dispersing by heating and then drying.

[0014] The black organic-inorganic hybrid ink of this invention, formulated by compounding carbon black, copper chromate black, aluminum dihydrogen phosphate and kaolin, produces a black pigment with good opacity and high temperature resistance, as well as good adhesion to the substrate. Furthermore, the raw materials have good compatibility and the components work synergistically, enabling the black organic-inorganic hybrid ink to withstand temperatures up to 500°C. The printed ink layer has high hardness and good adhesion to the substrate, and is suitable for various substrates and printing processes.

[0015] Optionally, the organic-inorganic hybrid resin may be an organosilicon hybrid resin or a polyester-modified organosilicon resin, etc.

[0016] Optionally, the silicone resin may be selected from methylphenyl polysiloxane resins, etc. Silicone resins provide beneficial heat resistance, corrosion resistance, and moisture resistance.

[0017] Preferably, the dilution film-forming control agent is selected from ethylene glycol tert-butyl ether, xylene, or n-butyl ester, which can be used to control ink layer thickness and cost, and is convenient to apply, saving labor and materials.

[0018] Preferably, in the preparation process of the black pigment, ethanol and water are mixed in a ratio of 1:3-5 to prepare a mixed solution of water and ethanol, the heating temperature is 50-100℃, and the heating time is 1-1.5h; a disperser is used to stir during the dispersion process to prevent agglomeration.

[0019] Preferably, the filler is boron carbide, silicon carbide, silicon nitride, or spodumene. These fillers are used to enhance the hardness of the ink layer.

[0020] Optionally, the leveling agent is tributyl phosphate or polyether-modified polydimethylsiloxane, which can be used to improve surface leveling, scratch resistance and gloss.

[0021] Optionally, the anti-settling agent is fumed silica and / or bentonite.

[0022] Optionally, the defoamer may be polyoxypropylene, polyether defoamer, modified polyether defoamer, etc.

[0023] This invention also provides a method for preparing the aforementioned black organic-inorganic hybrid ink, comprising the following steps:

[0024] The organic-inorganic hybrid resin, organosilicon resin, dilution film-forming control agent, mica powder, black pigment, filler, leveling agent, anti-settling agent and defoamer are mixed according to the selected weight parts, and then dispersed by high-speed stirring. After grinding, the black organic-inorganic hybrid ink is prepared.

[0025] Preferably, the stirring speed is 1500-2500 r / min.

[0026] Preferably, the grinding process uses a three-roll mill to grind for 3-5 passes. The particle diameter is set to 0.1μm for the first pass, 0.09μm for the second pass, 0.07μm for the third pass, 0.05μm for the fourth pass, and 0.03μm for the fifth pass.

[0027] The present invention also provides the application of the aforementioned black organic-inorganic hybrid ink in the printing field.

[0028] The present invention also provides a method for printing using the aforementioned black organic-inorganic hybrid ink, wherein the printing substrate is metal or glass, and the ink is sprayed or screen-printed on the substrate and then cured.

[0029] Furthermore, the glass is preferably soda-lime glass or borosilicate glass. The black organic-inorganic hybrid ink is screen-printed using a 200-500 mesh screen, with the printing thickness maintained at 5-10 μm. Then, it is baked at a high temperature of 280-330℃ for 25-35 minutes to cure and form the final product, thus completing the printing process.

[0030] This black organic-inorganic hybrid ink, when printed on soda-lime glass or borosilicate glass, forms a high-temperature resistant, high-hardness black surface coating. The maximum temperature resistance can reach 500℃, the pencil hardness can reach 5H, and the surface adhesion test can reach level 0. After passing the international standard cross-cut adhesion test, the ink showed no peeling after being removed with 3M tape.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] (1) The present invention uses a specific ratio of carbon black, copper chromium black, aluminum dihydrogen phosphate and kaolin to prepare a black pigment and apply it to ink. The black pigment has good hiding power and high temperature resistance.

[0033] (2) The black organic-inorganic hybrid ink provided by the present invention belongs to the category of medium temperature ink. It is an alcohol-soluble ink with a maximum temperature resistance of 500℃, a pencil hardness of 2-5H, and a surface adhesion test that meets ISO2409 and GB / T9286-1998 standards, with a maximum grade of 0. After the international standard cross-cut adhesion test, the ink did not peel off after the 3M tape was removed.

[0034] (3) The black organic-inorganic hybrid ink provided by the present invention has good versatility and is suitable for a variety of substrate surfaces, such as soda-lime glass, high borosilicate glass, stainless steel, aluminum, etc. It is also suitable for a variety of printing processes and can meet environmental protection requirements, and has good market prospects. Attached Figure Description

[0035] Figure 1 The graphs show the pencil hardness test results and adhesion test results of the black organic-inorganic hybrid ink in Example 1.

[0036] Figure 2 The graph shows the pencil hardness test results and adhesion test results of the black organic-inorganic hybrid ink in Example 2.

[0037] Figure 3 The graphs show the pencil hardness test results and adhesion test results of the black organic-inorganic hybrid ink in Example 3. Detailed Implementation

[0038] The present invention will be further illustrated below with reference to the embodiments and accompanying drawings. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Operating methods not specifically specified in the following embodiments are generally performed under conventional conditions or as recommended by the manufacturer.

[0039] Organosilicon hybrid resins, polyester-modified organosilicon resins, and methylphenyl polysiloxane resins can be purchased in domestic and international markets, such as Jiangsu Sanmu Group Co., Ltd. and Changzhou Jianuo Organosilicon Co., Ltd.

[0040] Example 1

[0041] The black organic-inorganic hybrid ink in this embodiment is made from the following raw materials in parts by weight: 44 parts of polyester modified silicone resin; 7 parts of methylphenyl polysiloxane resin; 9 parts of xylene dilution film-forming control agent; 9 parts of mica powder; 26 parts of black pigment; 1.5 parts of silicon nitride filler; 1 part of polyether modified polydimethylsiloxane leveling agent; 1 part of fumed silica; 1 part of bentonite; 0.5 parts of polyoxypropylene defoamer; wherein, the black pigment is made by dissolving 7 parts of carbon black, 10 parts of copper chromium black, 7 parts of aluminum dihydrogen phosphate and 2 parts of kaolin in a mixed solution of water and ethanol (water:ethanol = 1:4), heating at 70°C for 1 hour, while stirring and dispersing with a disperser to prevent agglomeration, and then drying at 150°C.

[0042] According to the above formula, the organic-inorganic hybrid resin, organosilicon resin, dilution film-forming control agent, mica powder, black pigment, filler, leveling agent, fumed silica, bentonite and defoamer are mixed and dispersed at 2000 r / min, and then ground three times using a three-roll mill. The particle diameter is set to 0.1 μm for the first pass, 0.09 μm for the second pass, and 0.07 μm for the third pass to prepare the black organic-inorganic hybrid ink.

[0043] Example 2

[0044] The black organic-inorganic hybrid ink in this embodiment is made from the following raw materials in parts by weight: 46 parts of organosilicon hybrid resin; 8.5 parts of methylphenyl polysiloxane resin; 8 parts of ethylene glycol tert-butyl ether dilution film-forming control agent; 7.8 parts of mica powder; 24.5 parts of black pigment; 1.7 parts of silicon carbide filler; 1 part of tributyl phosphate leveling agent; 1 part of fumed silica; 1 part of bentonite; and 0.5 parts of polyoxypropylene defoamer. The black pigment is prepared by dissolving 6 parts of carbon black, 10 parts of copper chromate black, 7 parts of aluminum dihydrogen phosphate, and 1 part of kaolin in a mixed solution of water and ethanol (water:ethanol = 1:4), heating at 70°C for 1 hour, and simultaneously stirring and dispersing with a disperser to prevent agglomeration, followed by drying at 150°C.

[0045] According to the above formula, the organic-inorganic hybrid resin, organosilicon resin, dilution film-forming control agent, mica powder, black pigment, filler, leveling agent, fumed silica, bentonite and defoamer are mixed and dispersed at 2300 r / min, and then ground three times using a three-roll mill. The particle diameter is set to 0.1 μm for the first pass, 0.09 μm for the second pass, and 0.07 μm for the third pass to prepare the black organic-inorganic hybrid ink.

[0046] Example 3

[0047] The black organic-inorganic hybrid ink in this embodiment is made from the following raw materials in parts by weight: 48 parts of polyester modified silicone resin; 8 parts of methyl phenyl polysiloxane resin; 8 parts of ethylene glycol tert-butyl ether dilution film-forming control agent; 8 parts of mica powder; 22.5 parts of black pigment; 2 parts of boron carbide filler; 1 part of tributyl phosphate leveling agent; 1 part of fumed silica; 1 part of bentonite; and 0.5 parts of polyether defoamer. The black pigment is prepared by dissolving 6 parts of carbon black, 8 parts of copper chromate black, 7 parts of aluminum dihydrogen phosphate, and 1.5 parts of kaolin in a mixed solution of water and ethanol (water:ethanol = 1:4), heating at 70°C for 1 hour, and simultaneously stirring and dispersing with a disperser to prevent agglomeration, followed by drying at 150°C.

[0048] According to the above formula, the organic-inorganic hybrid resin, organosilicon resin, dilution film-forming control agent, mica powder, black pigment, filler, leveling agent, fumed silica, bentonite and defoamer are mixed and dispersed at 2500 r / min. After grinding five times, the particle diameter is set to 0.1 μm for the first grinding, 0.09 μm for the second grinding, 0.07 μm for the third grinding, 0.05 μm for the fourth grinding, and 0.03 μm for the fifth grinding, thus preparing the black organic-inorganic hybrid ink.

[0049] Comparative Example 1

[0050] The only difference between the ink in this comparative example and the black organic-inorganic hybrid ink in Example 1 is that the amount of methylphenyl polysiloxane resin is 51 parts.

[0051] Sample Analysis

[0052] The inks prepared in Examples 1-3 and Comparative Example 1 were tested. The inks were printed using a 300-mesh screen, with the printing thickness maintained at approximately 8 μm. Then, they were baked at 280°C for 30 minutes to cure and complete the printing process.

[0053] The heat resistance test was a destructive experiment. The printed glass was placed in a high-temperature, constant-temperature oven for 30 minutes, then removed and 500ml of room-temperature cold water was poured over the entire glass surface from a distance. If the glass did not crack or deform, and the printed color showed no significant change, it passed the test. The hardness of the ink layer was tested using the pencil hardness test method, and the surface adhesion was tested according to GB / T9286-1998. The results are shown in Tables 1 and 2, respectively. Figure 1-3 As shown.

[0054] Table 1. Performance test results of inks prepared in Examples 1-3 and Comparative Example 1

[0055]

[0056] The above results show that the black organic-inorganic hybrid ink prepared by this invention has better heat resistance than commercially available ordinary medium-temperature inks, and its pencil hardness reaches 5H, while its surface adhesion can reach level 0.

[0057] The embodiments described above provide a detailed explanation of the technical solutions of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, additions, or similar substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A black organic-inorganic hybrid ink, characterized in that, Made from the following parts by weight of raw materials: 40-50 parts of organic-inorganic hybrid resin; 5-10 parts of silicone resin; Dilute the film-forming control agent to 8-10 parts; 5-10 parts mica powder; 20-26 parts black pigment; 1-3 parts of filler; Leveling agent 0.5-1.5 parts; 2-4 parts of anti-settling agent; 0.2-0.5 parts of defoamer; The black pigment is prepared by dissolving 5-8 parts carbon black, 8-10 parts copper chromium black, 5-8 parts aluminum dihydrogen phosphate and 1-2 parts kaolin in a mixed solution of water and ethanol, dispersing it by heating, and then drying it. The organic-inorganic hybrid resin is an organosilicon hybrid resin or a polyester-modified organosilicon resin; The organosilicon resin is a methylphenyl polysiloxane resin; In the preparation process of the black pigment, the heating temperature is 50-100℃ and the heating time is 1-1.5h; a disperser is used to stir during the dispersion process to prevent agglomeration. The anti-settling agent is fumed silica and / or bentonite.

2. The black organic-inorganic hybrid ink according to claim 1, characterized in that, The dilution film-forming control agent is selected from ethylene glycol tert-butyl ether, xylene, or n-butyl ester.

3. The black organic-inorganic hybrid ink according to claim 1, characterized in that, The filler is boron carbide, silicon carbide, silicon nitride, or spodumene.

4. The method for preparing black organic-inorganic hybrid ink according to any one of claims 1-3, characterized in that, Includes the following steps: The organic-inorganic hybrid resin, organosilicon resin, dilution film-forming control agent, mica powder, black pigment, filler, leveling agent, anti-settling agent and defoamer are mixed according to the selected weight parts, and then dispersed by high-speed stirring. After grinding, the black organic-inorganic hybrid ink is prepared.

5. The application of the black organic-inorganic hybrid ink according to any one of claims 1-3 in the printing field.

6. A method for printing using the black organic-inorganic hybrid ink according to any one of claims 1-3, characterized in that, The printing substrate is soda-lime glass or borosilicate glass. The black organic-inorganic hybrid ink is printed using a 200-500 mesh screen, with the printing thickness maintained at 5-10 μm. Then, it is baked at a high temperature of 280-330℃ for 25-35 minutes to cure and form the final product.

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