A method for preparing high-temperature resistant ink

Abstract

This invention discloses a method for preparing a high-temperature resistant ink, belonging to the field of ink technology. The tin-alkyl organosilicon resin prepared by this invention can increase the crosslinking density of the ink, further enhancing its heat resistance. The amino-acrylic acid addition reaction of 3-(methacryloyloxy)propyltrimethoxysilane and 2-aminodiphenyl sulfide forms stable silicon-nitrogen bonds. The formation of these silicon-nitrogen bonds helps to improve the bonding force between the silane and ink molecules, thereby improving the overall thermal stability of the ink. Tin alkylamines can increase the crosslinking density of the ink, further enhancing its heat resistance. The ink of this invention has excellent heat resistance, with an adhesion grade of 1. After firing at 500℃, the ink surface remains good, without cracking, reduced adhesion, peeling, color change, or edge cracking.

Description

Technical Field

[0001] This invention relates to the field of ink technology, and in particular to a method for preparing a high-temperature resistant ink. Background Technology

[0002] Currently, various household appliances are widely used, and some appliances can operate at temperatures up to 300℃, or even instantaneously up to 500℃, placing higher demands on protective and decorative inks. High-temperature resistant inks are mainly composed of binders, pigments, fillers, and additives. These components are mixed in a certain proportion according to requirements and processed into inks through wetting, dispersion, grinding, and other processes.

[0003] Chinese Patent CN116694136A: Provides a manufacturing process and method for an environmentally friendly high-temperature resistant ink, relating to the field of printing ink preparation technology. The formulation of this environmentally friendly high-temperature resistant ink comprises the following raw materials in parts by weight: 50-80 parts water-based acrylic resin, 26-52 parts methyl methacrylate, 20-46 parts polyurethane, 8-14 parts organic pigment, 3-8 parts heat-resistant additive, 10-18 parts chloroacetic acid resin, 1-5 parts lemon chrome yellow, 4-16 parts titanium dioxide, 6-10 parts modified polyurethane adhesive, 54-76 parts environmentally friendly reactive dye, 4-8 parts water-based dispersing defoamer, 1-4 parts thickener, 5-12 parts chelating agent, 3-8 parts smoothing agent, and 12-18 parts solvent. The ink of this invention has the characteristics of high gloss, good leveling, and excellent printing color development performance. It also has low viscosity, which makes it less likely to cause paper lint or dirt during printing. It dries quickly, does not contain solvents such as benzene and ketone, and has little solvent residue, which meets the requirements of human safety and environmental protection. In addition, it has strong high temperature resistance, which can withstand temperatures above 180°C and does not fade when heat-sealed.

[0004] Chinese Patent CN115820033A relates to the field of chip printing ink technology, and more specifically, to a high-temperature resistant ink for chip screen printing and its preparation method. The high-temperature resistant ink for chip screen printing is prepared from the following raw materials in parts by weight: 50-60 parts of silicone resin, 10-20 parts of epoxy resin, 2-6 parts of curing agent, 2-8 parts of additives, 40-60 parts of solvent, and 0-5 parts of pigment. The high-temperature resistant ink for chip screen printing prepared using the above raw materials has good high-temperature resistance and adhesion properties, and the ink is not easily discolored or peeled off during chip use.

[0005] Chinese Patent CN115260837B: Provides a method for treating pigments and a water-based high-temperature resistant ink composition, relating to the field of ink technology. The pigment treatment method includes treating ultrafine glass powder with a first silane coupling agent to obtain modified ultrafine glass powder; treating inorganic pigments with a second silane coupling agent to obtain modified inorganic pigments; treating nano-titanium dioxide with a third silane coupling agent to obtain modified titanium dioxide; dispersing the modified ultrafine glass powder, modified inorganic pigments, and modified titanium dioxide in water, stirring and reacting to obtain a pigment dispersion. This invention uses nano-titanium dioxide as a dispersant for ultrafine glass powder and / or inorganic pigments, achieving a relatively stable dispersion effect without the need for additional dispersants or anti-settling agents, obtaining a stable pigment dispersion. Applied to water-based high-temperature resistant ink compositions as markings during the annealing process of cold-rolled steel sheets, the coating exhibits good adhesion, clear color, and less yellowing after annealing.

[0006] The inks prepared by the above patents and existing technologies will exhibit the following phenomena on the ink surface under high temperature: cracking, reduced adhesion, peeling, color change, and edge cracking; after long-term use, ink peeling may even occur. Summary of the Invention

[0007] Therefore, it is necessary to provide a method for preparing high-temperature resistant inks to address the problems of cracking, reduced adhesion, peeling, color change, and edge cracking that occur in inks prepared by existing technologies at high temperatures.

[0008] To address the above problems, this invention provides a method for preparing a high-temperature resistant ink, the steps of which are as follows:

[0009] S1: Weigh 60-80 parts by weight of tin-alkyl organosilicon resin and 1-5 parts by weight of nano-silica, and disperse them in a dispersion mill at 1000-2000 rpm for 10-20 minutes;

[0010] S2: Add 5-10 parts of pigment and continue stirring for 20-40 minutes;

[0011] S3: Continue to add 0.01-0.1 parts of defoamer and 0.01-0.1 parts of leveling agent, mix evenly, and obtain high temperature resistant ink.

[0012] According to some embodiments of the present invention, the defoamer is polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane, or polyether-modified silicone defoamer.

[0013] According to some embodiments of the present invention, the leveling agent is silicone oil, polydimethylsiloxane, polymethylalkylsiloxane, polyether polyester modified organosiloxane, or alkyl modified organosiloxane.

[0014] According to some embodiments of the present invention, the preparation method of the tin-containing alkyl organosilicon resin is as follows:

[0015] H1: Weigh 60-70 parts by weight of methyltrimethoxysilane and 10-15 parts by weight of tin-containing alkylpropyltrimethoxysilane, add them to the reaction vessel, add 80-100 parts by weight of solvent, start stirring, heat to 60-80℃, add 40-50 parts by weight of deionized water dropwise over 5-10 minutes; after the addition is complete, react for 3-5 hours.

[0016] H2: After the reaction is complete, evaporate the water and solvent, cool to room temperature, add 1-3 parts of diethylene glycol butyl ether and 1-3 parts of curing agent, stir evenly, and obtain tin-containing alkyl organosilicon resin.

[0017] According to some embodiments of the present invention, the solvent is one of methanol, ethanol, and acetone.

[0018] According to some embodiments of the present invention, the curing agent is one of diethylenetriamine and ethylenediamine.

[0019] According to some embodiments of the present invention, the method for preparing the tin-containing alkylpropyltrimethoxysilane is as follows:

[0020] By weight, add 2-5 parts of 2-aminodiphenyl sulfide, 0.01-0.2 parts of (Z)-3-tributyltin alkyl acrylate, 20-30 parts of methanol, and 2-5 parts of diethanolamine to a reaction vessel, stir at 60-70°C for 120-180 minutes, and remove methanol by distillation; then add 70-100 parts of 3-(methacryloyloxy)propyltrimethoxysilane, stir at 60-70°C for 20-60 minutes, and the reaction is completed to obtain tin-containing alkylpropyltrimethoxysilane.

[0021] The reaction mechanism of tin-containing alkylpropyltrimethoxysilane is as follows:

[0022] (Z)-3-Tributyltin alkyl acrylate undergoes an amino-acrylic acid addition reaction with 2-aminodiphenyl sulfide; 3-(methacryloyloxy)propyltrimethoxysilane undergoes an amino-acrylic acid addition reaction with 2-aminodiphenyl sulfide to obtain tin-containing alkyltrimethoxysilane. This can improve the high-temperature resistance of silicone inks. Tin alkyl acrylate readily reacts with amino groups under heating conditions, usually by opening the tin alkyl five-membered ring to form tin alkylamines. In this process, the organic part of tin (tributyl) combines with the amino part of aminodiphenyl sulfide to form tin alkylamines. Because these chemical reactions increase the crosslinking density and thermal stability of the ink, these inks may also exhibit better mechanical properties. In addition, due to the presence of silane, the ink also has better water and chemical resistance. In summary, these chemical reactions improve the high-temperature resistance of inks by enhancing the stability and durability of the ink at the molecular level.

[0023] The present invention provides a method for preparing a high-temperature resistant ink, which, compared with the prior art, has the following significant advantages:

[0024] 1. The present invention adds nano-silica to ink, which can improve the thixotropy, emulsification and suspension stability of ink, and has the effects of thickening and matting; the nano-silica is fully and uniformly dispersed in tin-alkyl organosilicon resin, which can comprehensively improve the strength, toughness and ductility of ink, making the surface more dense and smooth.

[0025] 2. The tin-containing alkyl organosilicon resin prepared by this invention can increase the crosslinking density of the ink and further enhance its heat resistance; the amino-acrylic acid addition reaction of 3-(methacryloyloxy)propyltrimethoxysilane and 2-aminodiphenyl sulfide forms a stable silicon-nitrogen bond; the formation of this silicon-nitrogen bond helps to improve the binding force between silane and ink molecules, thereby improving the overall thermal stability of the ink; tin alkylamine can increase the crosslinking density of the ink and further enhance its heat resistance.

[0026] 3. The ink of the present invention has excellent heat resistance and adhesion grade 1. After firing at 500°C, the ink surface is good and there are no cracks, reduced adhesion, peeling, color changes, or edge cracking. Attached Figure Description

[0027] Figure 1 The image shows a printed product of the high-temperature resistant ink prepared in Example 3. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that these descriptions are merely exemplary and not intended to limit the scope of the invention. Furthermore, descriptions of well-known structures and technologies are omitted in the following description to avoid unnecessarily obscuring the concept of the invention.

[0029] The evaluation method in the specific implementation plan of this case is as follows:

[0030] The glass slide is degreased, cleaned, and dried. The ink prepared in this invention is then screen-printed onto the treated glass slide using a 200-mesh screen printing plate. The slide is then placed in a constant temperature drying oven for curing.

[0031] 1. Heat resistance test: Set the box-type resistance furnace to 500℃, put the test piece into the furnace, keep it at that temperature for one hour, take it out and cool it to room temperature, and observe the surface condition of the coating with a magnifying glass: if there is no cracking, reduced adhesion, peeling, color change, or edge cracking, it indicates that the coating performance is good.

[0032] 2. Adhesion test: The test shall be conducted in accordance with GB / T1720-1979.

[0033] Example 1

[0034] A method for preparing a high-temperature resistant ink, comprising the following steps:

[0035] S1: Weigh 60g of tin-containing alkyl organosilicon resin and 1g of nano-silica, and disperse them in a dispersion mill at 1000 rpm for 10 min;

[0036] S2: Add 5g of pigment and continue stirring for 20 minutes;

[0037] S3: Continue to add 0.01g of defoamer and 0.01g of leveling agent, mix evenly, and obtain high-temperature resistant ink.

[0038] The defoamer mentioned is a polyoxypropylene glycerol ether defoamer.

[0039] The leveling agent is silicone oil.

[0040] The preparation method of the tin-containing alkyl organosilicon resin is as follows:

[0041] H1: Weigh 60g of methyltrimethoxysilane and 10g of tin-containing alkylpropyltrimethoxysilane, add them to the reaction vessel, add 80g of solvent, start stirring, heat to 60℃, add 40g of deionized water dropwise over 5min; after the addition is complete, react for 3h.

[0042] H2: After the reaction is complete, evaporate the water and solvent, cool to room temperature, add 1g of diethylene glycol butyl ether and 1g of curing agent, stir evenly, and obtain tin-containing alkyl organosilicon resin.

[0043] The solvent is methanol.

[0044] The curing agent is diethylenetriamine.

[0045] The method for preparing the tin-containing alkylpropyltrimethoxysilane is as follows:

[0046] 2g of 2-aminodiphenyl sulfide, 0.01g of (Z)-3-tributyltin alkyl acrylate, 20g of methanol, and 2g of diethanolamine were added to a reaction vessel and stirred at 60°C for 120 minutes. The methanol was then removed by distillation. 70g of 3-(methacryloyloxy)propyltrimethoxysilane was then added and stirred at 60°C for 20 minutes. The reaction was completed to obtain tin-containing alkylpropyltrimethoxysilane.

[0047] Example 2

[0048] A method for preparing a high-temperature resistant ink, comprising the following steps:

[0049] S1: Weigh 65g of tin-containing alkyl organosilicon resin and 2g of nano-silica, and disperse them in a dispersion mill at 1400 rpm for 15 min;

[0050] S2: Add 6g of pigment and continue stirring for 25 minutes;

[0051] S3: Continue to add 0.05g of defoamer and 0.05g of leveling agent, mix evenly, and obtain high-temperature resistant ink.

[0052] The defoamer mentioned is a polyoxypropylene polyoxyethylene glycerol ether defoamer.

[0053] The leveling agent is polydimethylsiloxane.

[0054] The preparation method of the tin-containing alkyl organosilicon resin is as follows:

[0055] H1: Weigh 63g of methyltrimethoxysilane and 12g of tin-containing alkylpropyltrimethoxysilane, add them to the reaction vessel, add 85g of solvent, start stirring, heat to 65℃, add 44g of deionized water dropwise over 6min; after the addition is complete, react for 4h.

[0056] H2: After the reaction is complete, evaporate the water and solvent, cool to room temperature, add 2g of diethylene glycol butyl ether and 2g of curing agent, stir evenly, and obtain tin-containing alkyl organosilicon resin.

[0057] The solvent is ethanol.

[0058] The curing agent is diethylenetriamine.

[0059] The method for preparing the tin-containing alkylpropyltrimethoxysilane is as follows:

[0060] 3g of 2-aminodiphenyl sulfide, 0.1g of (Z)-3-tributyltin alkyl acrylate, 24g of methanol, and 3g of diethanolamine were added to a reaction vessel and stirred at 65°C for 140 minutes. The methanol was then removed by distillation. 80g of 3-(methacryloyloxy)propyltrimethoxysilane was then added and stirred at 65°C for 30 minutes. The reaction was completed to obtain tin-containing alkylpropyltrimethoxysilane.

[0061] Example 3

[0062] A method for preparing a high-temperature resistant ink, comprising the following steps:

[0063] S1: Weigh 75g of tin-containing alkyl organosilicon resin and 4g of nano-silica, and disperse them in a dispersion mill at 1800 rpm for 15 min;

[0064] S2: Add 8g of pigment and continue stirring for 35 minutes;

[0065] S3: Continue to add 0.08g of defoamer and 0.08g of leveling agent, mix evenly, and obtain high-temperature resistant ink.

[0066] The defoamer mentioned is a polydimethylsiloxane defoamer.

[0067] The leveling agent is polymethylalkylsiloxane.

[0068] The preparation method of the tin-containing alkyl organosilicon resin is as follows:

[0069] H1: Weigh 68g of methyltrimethoxysilane and 14g of tin-containing alkylpropyltrimethoxysilane, add them to the reaction vessel, add 95g of solvent, start stirring, heat to 75℃, add 48g of deionized water dropwise over 8min; after the addition is complete, react for 4h.

[0070] H2: After the reaction is complete, evaporate the water and solvent, cool to room temperature, add 2g of diethylene glycol butyl ether and 2g of curing agent, stir evenly, and obtain tin-containing alkyl organosilicon resin.

[0071] The solvent is ethanol.

[0072] The curing agent is ethylenediamine.

[0073] The method for preparing the tin-containing alkylpropyltrimethoxysilane is as follows:

[0074] 4g of 2-aminodiphenyl sulfide, 0.15g of (Z)-3-tributyltin alkyl acrylate, 28g of methanol, and 4g of diethanolamine were added to a reaction vessel and stirred at 65°C for 160 minutes. The methanol was then removed by distillation. 90g of 3-(methacryloyloxy)propyltrimethoxysilane was then added and stirred at 65°C for 50 minutes. The reaction was completed to obtain tin-containing alkylpropyltrimethoxysilane.

[0075] Example 4

[0076] A method for preparing a high-temperature resistant ink, comprising the following steps:

[0077] S1: Weigh 80g of tin-containing alkyl organosilicon resin and 5g of nano-silica, and disperse them in a dispersion mill at 2000 rpm for 20 minutes;

[0078] S2: Add 10g of pigment and continue stirring for 40 minutes;

[0079] S3: Continue to add 0.1g of defoamer and 0.1g of leveling agent, mix evenly, and obtain high-temperature resistant ink.

[0080] The defoamer mentioned is a polyether-modified silicone defoamer.

[0081] The leveling agent is an alkyl-modified organosiloxane.

[0082] The preparation method of the tin-containing alkyl organosilicon resin is as follows:

[0083] H1: Weigh 70g of methyltrimethoxysilane and 15g of tin-containing alkylpropyltrimethoxysilane, add them to the reaction vessel, add 100g of solvent, start stirring, heat to 80℃, add 50g of deionized water dropwise over 10min; after the addition is complete, react for 5h.

[0084] H2: After the reaction is complete, evaporate the water and solvent, cool to room temperature, add 3g of diethylene glycol butyl ether and 3g of curing agent, stir evenly, and obtain tin-containing alkyl organosilicon resin.

[0085] The solvent is acetone.

[0086] The curing agent is ethylenediamine.

[0087] The method for preparing the tin-containing alkylpropyltrimethoxysilane is as follows:

[0088] 5g of 2-aminodiphenyl sulfide, 0.2g of (Z)-3-tributyltin alkyl acrylate, 30g of methanol, and 5g of diethanolamine were added to a reaction vessel and stirred at 70°C for 180 minutes. The methanol was then removed by distillation. 100g of 3-(methacryloyloxy)propyltrimethoxysilane was then added and stirred at 70°C for 60 minutes. The reaction was completed to obtain tin-containing alkylpropyltrimethoxysilane.

[0089] Comparative Example 1

[0090] In this example, tin-containing alkylpropyltrimethoxysilane is not added; otherwise, it is the same as in Example 1.

[0091] Comparative Example 2

[0092] In this example, 3-(methacryloyloxy)propyltrimethoxysilane is not added; otherwise, it is the same as in Example 1.

[0093] Comparative Example 3

[0094] In this example, 2-aminodiphenyl sulfide is not added, and everything else is the same as in Example 1.

[0095] Example evaluation results:

[0096] Heat resistance Adhesion Example 1 Good surface Level 2 Example 2 Good surface Level 2 Example 3 Good surface Level 1 Example 4 Good surface Level 1 Comparative Example 1 Surface cracking Level 5 Comparative Example 2 Edge cracking Level 4 Comparative Example 3 Slight cracks at the edges Level 3

[0097] Based on the data analysis of the above embodiments and comparative examples, the tin-containing alkyl organosilicon resin of the present invention can improve the heat resistance of inks.

[0098] It should be understood that the specific embodiments described above are merely illustrative or explanatory of the principles of the invention and do not constitute a limitation thereof. Therefore, any modifications, equivalent substitutions, improvements, etc., made without departing from the spirit and scope of the invention should be included within the protection scope of the invention. Furthermore, the appended claims are intended to cover all variations and modifications falling within the scope and boundaries of the appended claims, or equivalent forms of such scope and boundaries.

Claims

1. A method for preparing a high-temperature resistant ink, comprising the following steps: S1: Weigh 60-80 parts by weight of tin-alkyl organosilicon resin and 1-5 parts by weight of nano-silica, and disperse them in a dispersion mill at 1000-2000 rpm for 10-20 minutes; S2: Add 5-10 parts of pigment and continue stirring for 20-40 minutes; S3: Continue to add 0.01-0.1 parts of defoamer and 0.01-0.1 parts of leveling agent, mix evenly, and obtain high-temperature resistant ink; The preparation method of the tin-containing alkyl organosilicon resin is as follows: H1: Weigh 60-70 parts by weight of methyltrimethoxysilane and 10-15 parts by weight of tin-containing alkylpropyltrimethoxysilane, add them to the reaction vessel, add 80-100 parts by weight of solvent, start stirring, heat to 60-80℃, add 40-50 parts by weight of deionized water dropwise over 5-10 minutes; after the addition is complete, react for 3-5 hours. H2: After the reaction is complete, evaporate the water and solvent, cool to room temperature, add 1-3 parts of diethylene glycol butyl ether and 1-3 parts of curing agent, stir evenly to obtain tin-containing alkyl organosilicon resin; The method for preparing the tin-containing alkylpropyltrimethoxysilane is as follows: By weight, add 2-5 parts of 2-aminodiphenyl sulfide, 0.01-0.2 parts of (Z)-3-tributyltin alkyl acrylate, 20-30 parts of methanol, and 2-5 parts of diethanolamine to a reaction vessel, stir at 60-70°C for 120-180 minutes, and remove methanol by distillation; then add 70-100 parts of 3-(methacryloyloxy)propyltrimethoxysilane, stir at 60-70°C for 20-60 minutes, and the reaction is completed to obtain tin-containing alkylpropyltrimethoxysilane.

2. The method for preparing a high-temperature resistant ink according to claim 1, characterized in that: The defoamer is polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane, or polyether-modified silicone defoamer.

3. The method for preparing a high-temperature resistant ink according to claim 1, characterized in that: The leveling agent is silicone oil, polyether polyester modified organosiloxane, or alkyl modified organosiloxane.

4. The method for preparing a high-temperature resistant ink according to claim 1, characterized in that: The solvent is one of methanol, ethanol, and acetone.

5. The method for preparing a high-temperature resistant ink according to claim 1, characterized in that: The curing agent is one of diethylenetriamine and ethylenediamine.

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