Special chip identification high-resistance pad printing ink and preparation method thereof

Abstract

This invention relates to the field of ink technology, specifically to a high-durability pad printing ink for special chip marking and its preparation method. The high-durability pad printing ink for special chip marking is composed of the following raw materials in parts by weight: 10-15 parts polyester resin, 15-20 parts silicone resin, 25-30 parts crosslinking agent, 10-15 parts copper chromate black, 0.8-1.2 parts fumed silica, 5-8 parts functional additives, 1-1.5 parts tetrafluoroethylene wax powder, 15-20 parts isoflurane, and 2-4 parts n-butanol. The high-durability pad printing ink for special chip marking prepared by this invention not only has excellent high-temperature resistance and chemical resistance, but also good oxidation resistance and scratch resistance, extending its service life to a certain extent while effectively ensuring its quality.

Description

Technical Field

[0001] This invention relates to the field of ink technology, specifically to a high-durability pad printing ink for special chip marking and its preparation method. Background Technology

[0002] After semiconductor chips are manufactured, they must be marked with information such as the chip model, production date, and manufacturer. One important method for chip marking is pad printing, which involves printing ink onto the chip. This method offers advantages such as high production efficiency and no damage to the chip's structure.

[0003] Some special-purpose chips, such as weapon-grade chips, will face high temperatures, high humidity, high salinity, ultra-low temperatures, and extreme high temperatures generated by friction with air during combat readiness and training for several years or even decades. If a malfunction occurs or a "dumb" situation arises during training, and the chip needs to be disassembled for analysis or to replace parts, it is necessary to identify it by the markings on the chip. Therefore, the ink used for marking on these special-purpose chips must be able to maintain its properties of not softening, not peeling off, not powdering, and not changing color, and the markings must be clear and identifiable when used for a long time in the above-mentioned harsh environments.

[0004] Currently, high-durability pad printing inks that can meet the requirements of such extreme environments mainly rely on imports, but they still have the following shortcomings in performance: 1. Insufficient high temperature resistance: The ink layer is prone to peeling and powdering in extreme high temperature environments above 300℃; 2. Poor antioxidant properties; prone to aging during long-term storage or use, leading to decreased adhesion. 3. Poor chemical resistance: Its resistance to salt spray and chemical reagents (such as alcohol and methyl ethyl ketone) cannot meet the long-term use requirements of special chips.

[0005] Therefore, the present invention provides a high-durability pad printing ink for special chip marking and a method for preparing the same, in order to solve the technical problems mentioned above. Summary of the Invention

[0006] The special high-durability pad printing ink for chip marking prepared by this invention not only has excellent high temperature resistance and chemical resistance, but also good oxidation resistance and scratch resistance. To a certain extent, it extends the service life of the chip while effectively ensuring its quality.

[0007] To achieve the above objectives, the present invention provides the following technical solution: A special high-durability pad printing ink for chip marking is composed of the following raw materials in parts by weight: 10-15 parts polyester resin, 15-20 parts silicone resin, 25-30 parts crosslinking agent, 10-15 parts copper chromate black, 0.8-1.2 parts fumed silica, 5-8 parts functional additives, 1-1.5 parts tetrafluoroethylene wax powder, 15-20 parts isoflurane and 2-4 parts n-butanol.

[0008] The role of polyester resin is to ensure the adhesion and high temperature resistance of the ink. The role of silicone resin is to impart ultra-high temperature resistance to ink; Crosslinking agents possess self-crosslinking properties, and their function is to ultimately harden the ink layer, achieving resistance to alcohol, methyl ethyl ketone (MEK), and high temperatures. Copper chromium black, as an inorganic pigment, serves to provide ink coloring, high-temperature resistance, and fade resistance. The role of fumed silica is to impart appropriate thixotropic properties to the ink, preventing undesirable phenomena such as "silicone flow" and "ink overflow" during printing; The function of tetrafluoroethylene wax powder with a particle size of 3-5μm is to improve the surface hardness and smoothness of ink. The role of isoflurone in the formulation is to adjust the viscosity of the ink, so that the ink has better fluidity; The role of n-butanol in the formulation is to prolong the ink storage time and optimize the ink removal properties of the pad printing head during high-speed printing.

[0009] Furthermore, the preparation method of the functional additive includes the following steps: 2,6-di-tert-butyl-p-cresol (0.2-0.3 times the mass of the modified inorganic substrate) is added to a DMF dispersion of 10-20 g / L modified inorganic substrate. After uniform dispersion, amino-terminated polydimethylsiloxane (5-8 times the mass of the modified inorganic substrate), dicyclohexylcarbodiimide (1.5-2 times the mass of the modified inorganic substrate), and N-hydroxybenzotriazole (1.2-1.5 times the mass of the modified inorganic substrate) are added. The mixture is reacted at 70-80℃ for 5-8 hours under nitrogen protection. The product is then filtered, and the filter cake is washed sequentially with DMF (N,N-dimethylformamide), distilled water, and ethanol, and then vacuum dried to obtain the final product. The inorganic substrate is a composite material with spherical cerium oxide as the "core" and nano-zirconia as the "shell."

[0010] Furthermore, the preparation method of the modified inorganic substrate is as follows: the inorganic substrate is dispersed in an 85-90wt% ethanol aqueous solution at a dosage ratio of 20-50g / L, 30-50% by weight of 3-aminopropyltriethoxysilane is added, the mixture is refluxed for 3-5 hours, the product is filtered, and the resulting filter cake is added to DMF at a mass of 10-15 times its mass. After ultrasonic dispersion for 3-5 minutes, 40-50% by weight of 3-octenyl-2,5-dihydrofurandione is added, and the mixture is then reacted at 40-50℃ for 5-8 hours. After the reaction is completed, the product is filtered, washed, and vacuum dried sequentially to obtain the final product.

[0011] Furthermore, the preparation method of the inorganic substrate is as follows: Zirconium nitrate and hexamethylenetetramine are added to an ethanol dispersion of 10-30 g / L spherical cerium oxide, mixed well, and the resulting mixture is refluxed and stirred for 3-5 h; after the reaction is completed, the product is subjected to solid-liquid separation, washing, drying and high-temperature calcination treatment in sequence to obtain the final product.

[0012] Furthermore, the concentration of zirconium nitrate in the mixed components is 0.1-0.3 mol / L, and the concentration of hexamethylenetetramine is 1-3 mol / L.

[0013] Furthermore, the high-temperature calcination temperature is set to 500-700℃, and the high-temperature calcination time is set to 2-4 hours.

[0014] Furthermore, the preparation method of spherical cerium oxide is as follows: Cerium nitrate, polyethylene glycol 400 and deionized water are mixed and stirred in a mass ratio of 1:30-35:8-12 until the mixture is clear, and then kept at 160-190℃ for 20-30h; after the reaction is complete, the product is naturally cooled to room temperature, and then filtered, washed, dried and calcined in sequence to obtain the product.

[0015] Furthermore, the drying temperature is set to 60-80℃, and the drying time is set to 10-15h.

[0016] Furthermore, the calcination temperature is set to 500-600℃, and the calcination time is set to 2-3h.

[0017] A method for preparing a high-durability pad printing ink for special chip marking includes the following steps:

[0018] Step 1: Weigh each raw material according to the ink formula ratio and put each raw material into a stainless steel kettle. Disperse at high speed at 800-1200r / min for 2-3 hours. The temperature during dispersion should be controlled below 70℃. The second step is to cool the mixture for 24 hours after it is evenly dispersed, and then grind it with a three-roll mill until the fineness is ≤10μm. After grinding, n-butanol is added to adjust the viscosity. The resulting ink has a viscosity of 9000-11000cP at 30℃. The third step is to test the ink obtained in step two. If it passes the test, it will be sealed and packaged to obtain the high-durability pad printing ink for special chip marking.

[0019] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention uses cerium nitrate, polyethylene glycol 400, and deionized water as raw materials to prepare spherical cerium oxide with a double-layer hollow structure. The obtained spherical cerium oxide is then dispersed in an ethanol dispersion, and zirconium nitrate and hexamethylenetetramine are added. After a chemical reaction, a relatively dense zirconium oxide film is coated onto the surface of the spherical cerium oxide, thus obtaining a core-shell inorganic substrate with spherical cerium oxide as the "core" and zirconium oxide as the "film." The double-layer hollow structure gives the spherical cerium oxide excellent high-temperature resistance, which, combined with the zirconium oxide film on its surface, results in an inorganic substrate with excellent high-temperature resistance.

[0020] 2. An inorganic substrate was dispersed in an ethanol-water solution and modified with 3-aminopropyltriethoxysilane to introduce reactive groups onto its surface. Then, 3-octenyl-2,5-dihydrofurandione was added, and the inorganic substrate was activated through a chemical reaction, yielding a modified inorganic substrate. The modified inorganic substrate was then dispersed in DMF, and 2,6-di-tert-butyl-p-cresol was added. After uniform dispersion, the 2,6-di-tert-butyl-p-cresol was uniformly dispersed and adsorbed onto the rough surface of the modified inorganic substrate. Then, an ammonia-terminated polydimethylsiloxane was added. Finally, under the action of dicyclohexylcarbodiimide and N-hydroxybenzotriazole, the ammonia-terminated polydimethylsiloxane underwent an amidation reaction with the relevant reactive groups on the surface of the modified inorganic substrate to form bonds. A large number of ammonia-terminated polydimethylsiloxane molecules intertwined on the surface of the modified inorganic substrate formed a dense and hydrophobic network structure.

[0021] 3. The network structure on the surface of the modified inorganic substrate can effectively anchor 2,6-di-tert-butyl-p-cresol adsorbed on the surface of the modified inorganic substrate, giving the prepared functional additives certain antioxidant properties. This can slow down the aging rate of the ink to a certain extent, extend its service life, and effectively ensure its quality.

[0022] Furthermore, the cavity formed between the network structure and the zirconia film constitutes the first thermal barrier, the zirconia film constitutes the second thermal barrier, and the spherical cerium oxide with a double-layer hollow structure constitutes the third thermal barrier. The high-temperature resistance of the prepared functional additive is significantly improved under the synergistic effect of the three thermal barriers.

[0023] In addition, because the outer layer of this functional additive is an amino-terminated polydimethylsiloxane forming a network structure, it has good compatibility with the raw materials and organic phases in inks, making it more uniformly dispersed and ensuring the quality of the prepared ink.

[0024] The special high-durability pad printing ink for chip marking prepared by this invention not only has excellent high temperature resistance and chemical resistance, but also good oxidation resistance and scratch resistance. To a certain extent, it extends the service life of the chip while effectively ensuring its quality. Attached Figure Description

[0025] Figure 1 A close-up photograph of the high-durability pad printing ink prepared in Example 1; Figure 2 A sample image of a customer's work showing the high-durability pad printing ink prepared in Example 1 printed on a chip; Figure 3 The images show physical samples of the high-durability pad printing inks prepared in each embodiment and comparative example. Figure 4 A photograph of the inorganic substrate prepared in Example 1; Figure 5 A photograph of the functional additive prepared in Example 1; Figure 6 A photograph of the high-durability pad printing ink prepared in Example 1 during a salt spray test. Detailed Implementation

[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] The sources of the raw materials used in the following examples are as follows: The polyester resin, model DYNAPOL® LH748-02LN (tentative version), was purchased from Wuxi Hengmao Science and Trade Co., Ltd. The silicone resin used was 7100 silicone resin, purchased from Shanghai Tumai Trading Co., Ltd. The crosslinking agent used was CYMEL325 resin, purchased from Shanghai Yuyiyuan New Materials Co., Ltd. The ammonia-terminated polydimethylsiloxane was purchased from Hubei Qifei Pharmaceutical Chemical Co., Ltd., with product number QF4885. Example 1:

[0028] A special high-durability pad printing ink for chip marking is composed of the following raw materials in parts by weight: 10 parts polyester resin, 15 parts silicone resin, 25 parts crosslinking agent, 10 parts copper chromate black, 0.8 parts fumed silica, 5 parts functional additives, 1 part tetrafluoroethylene wax powder, 15 parts isoflurone and 2 parts n-butanol.

[0029] The preparation method of the functional additive includes the following steps: 2,6-di-tert-butyl-p-cresol with a mass of 0.2 times that of the modified inorganic substrate is added to a DMF dispersion of 10 g / L modified inorganic substrate. After uniform dispersion, amino-terminated polydimethylsiloxane, dicyclohexylcarbodiimide, and N-hydroxybenzotriazole with masses of 5 times, 1.5 times, and 1.2 times respectively are added. The mixture is reacted at 70°C for 8 hours under nitrogen protection. The product is then filtered, and the filter cake is washed successively with DMF, distilled water, and ethanol, and then dried under vacuum to obtain the final product. The inorganic substrate is a composite material with spherical cerium oxide as the "core" and nano-zirconia as the "shell".

[0030] The modified inorganic substrate is prepared as follows: the inorganic substrate is dispersed in an 85wt% ethanol aqueous solution at a dosage ratio of 20g / L, 30% of the inorganic substrate is added, 3-aminopropyltriethoxysilane is added, the mixture is refluxed for 3h, the product is filtered, the resulting filter cake is added to DMF with a mass of 10 times its mass, ultrasonically dispersed for 3min, 40% of the filter cake is added, and then the mixture is reacted at 40℃ for 8h. After the reaction is completed, the product is filtered, washed and vacuum dried sequentially to obtain the final product.

[0031] The inorganic substrate is prepared by adding zirconium nitrate and hexamethylenetetramine to an ethanol dispersion of 10 g / L spherical cerium oxide, mixing well, and then refluxing and stirring the resulting mixture for 3 h. After the reaction is completed, the product is subjected to solid-liquid separation, washing, drying, and high-temperature calcination treatment to obtain the final product. The concentration of zirconium nitrate in the mixed components was 0.1 mol / L, and the concentration of hexamethylenetetramine was 1 mol / L; the high-temperature calcination temperature was set to 500℃, and the high-temperature calcination time was set to 4 h.

[0032] The preparation method of spherical cerium oxide is as follows: Cerium nitrate, polyethylene glycol 400 and deionized water are mixed and stirred in a mass ratio of 1:30:8 until the mixture is clear, and then kept at 160℃ for 30h; after the reaction is complete, the product is naturally cooled to room temperature, and then filtered, washed, dried and calcined in sequence to obtain the product. The drying temperature was set to 60℃ and the drying time to 15h; the calcination temperature was set to 500℃ and the calcination time to 3h.

[0033] A method for preparing a high-durability pad printing ink for special chip marking includes the following steps: Step 1: Weigh each raw material according to the ink formula ratio and put each raw material into a stainless steel kettle. Disperse at high speed for 2 hours at a speed of 800-1200 r / min. The temperature during dispersion should be controlled below 70℃. The second step is to cool the mixture for 24 hours after it is evenly dispersed, and then grind it to a fineness of 8μm using a three-roll mill. After grinding, n-butanol is added to adjust the viscosity. The resulting ink has a viscosity of 10000cP at 30℃. The third step is to test the ink obtained in step two. If it passes the test, it will be sealed and packaged to obtain the high-durability pad printing ink for special chip marking. Example 2:

[0034] The preparation method of the high-durability pad printing ink for special chip marking provided in this embodiment is basically the same as that in Example 1, and the preparation method of spherical cerium oxide is the same as that in Example 1. The difference lies in the specific ratio of the raw materials used and the preparation method of the functional additives. The specific ratio of each raw material and the preparation method of the functional additives in this embodiment are as follows: A special high-durability pad printing ink for chip marking is composed of the following raw materials in parts by weight: 12 parts polyester resin, 19 parts silicone resin, 27 parts crosslinking agent, 13 parts copper chromate black, 1 part fumed silica, 6 parts functional additives, 1.2 parts tetrafluoroethylene wax powder, 17 parts isoflurone and 3 parts n-butanol.

[0035] The preparation method of the functional additive includes the following steps: 2,6-di-tert-butyl-p-cresol with a mass of 0.25 times that of the modified inorganic substrate is added to a DMF dispersion of 15 g / L modified inorganic substrate. After uniform dispersion, amino-terminated polydimethylsiloxane, dicyclohexylcarbodiimide, and N-hydroxybenzotriazole with masses of 6 times, 1.5 times, and 1.4 times respectively are added. The mixture is reacted at 75°C for 6 hours under nitrogen protection. The product is then filtered, and the filter cake is washed successively with DMF, distilled water, and ethanol, and then dried under vacuum to obtain the final product. The inorganic substrate is a composite material with spherical cerium oxide as the "core" and nano-zirconia as the "shell".

[0036] The modified inorganic substrate is prepared as follows: the inorganic substrate is dispersed in an 85wt% ethanol aqueous solution at a dosage ratio of 30g / L, and 40% of the inorganic substrate is added with 3-aminopropyltriethoxysilane. After reflux reaction for 4h, the product is filtered, and the resulting filter cake is added to DMF with a mass of 10 times that mass. After ultrasonic dispersion for 4min, 45% of the filter cake is added with 3-octenyl-2,5-dihydrofurandione. Then, the reaction is carried out at 45℃ for 6h. After the reaction is completed, the product is filtered, washed and vacuum dried sequentially to obtain the final product.

[0037] The inorganic substrate is prepared by adding zirconium nitrate and hexamethylenetetramine to an ethanol dispersion of 20 g / L spherical cerium oxide, mixing well, and then refluxing and stirring the resulting mixture for 4 h. After the reaction is completed, the product is subjected to solid-liquid separation, washing, drying and high-temperature calcination treatment to obtain the final product. The concentration of zirconium nitrate in the mixed components was 0.2 mol / L, and the concentration of hexamethylenetetramine was 2 mol / L; the high-temperature calcination temperature was set to 600℃, and the high-temperature calcination time was set to 3 h. Example 3:

[0038] The preparation method of the high-durability pad printing ink for special chip marking provided in this embodiment is basically the same as that in Example 1, and the preparation method of spherical cerium oxide is the same as that in Example 1. The difference lies in the specific ratio of the raw materials used and the preparation method of the functional additives. The specific ratio of each raw material and the preparation method of the functional additives in this embodiment are as follows: A special high-durability pad printing ink for chip marking is composed of the following raw materials in parts by weight: 15 parts polyester resin, 20 parts silicone resin, 30 parts crosslinking agent, 15 parts copper chromium black, 1.2 parts fumed silica, 8 parts functional additives, 1.5 parts tetrafluoroethylene wax powder, 20 parts isoflurane and 4 parts n-butanol.

[0039] The preparation method of the functional additive includes the following steps: 2,6-di-tert-butyl-p-cresol with a mass of 0.3 times that of the modified inorganic substrate is added to a DMF dispersion of 20 g / L modified inorganic substrate. After uniform dispersion, amino-terminated polydimethylsiloxane, dicyclohexylcarbodiimide, and N-hydroxybenzotriazole with masses of 8 times, 2 times, and 1.5 times respectively are added. The mixture is reacted at 80°C for 5 h under nitrogen protection. The product is then filtered, and the filter cake is washed successively with DMF, distilled water, and ethanol, and then dried under vacuum to obtain the final product. The inorganic substrate is a composite material with spherical cerium oxide as the "core" and nano-zirconia as the "shell".

[0040] The modified inorganic substrate is prepared as follows: the inorganic substrate is dispersed in a 90wt% ethanol aqueous solution at a dosage ratio of 50g / L, and 3-aminopropyltriethoxysilane (50% by mass of the inorganic substrate) is added. After reflux reaction for 5h, the product is filtered, and the resulting filter cake is added to DMF with a mass of 15 times that mass. After ultrasonic dispersion for 5min, 3-octenyl-2,5-dihydrofurandione (50% by mass of the filter cake) is added, and then the reaction is carried out at 50℃ for 5h. After the reaction is completed, the product is filtered, washed and vacuum dried sequentially to obtain the final product.

[0041] The inorganic substrate is prepared by adding zirconium nitrate and hexamethylenetetramine to an ethanol dispersion of 30 g / L spherical cerium oxide, mixing well, and then refluxing and stirring the resulting mixture for 5 h. After the reaction is completed, the product is subjected to solid-liquid separation, washing, drying, and high-temperature calcination treatment to obtain the final product. The concentration of zirconium nitrate in the mixed components was 0.3 mol / L, and the concentration of hexamethylenetetramine was 3 mol / L; the high-temperature calcination temperature was set to 700℃, and the high-temperature calcination time was set to 2 h.

[0042] Comparative Example 1: The difference between this comparative example and Example 1 is that an equal amount of spherical cerium oxide is used to replace the functional additives in this comparative example.

[0043] Comparative Example 2: The difference between this comparative example and Example 1 is that an equal amount of inorganic substrate is used to replace the functional additives in this comparative example.

[0044] Comparative Example 3: The difference between this comparative example and Example 1 is that 2,6-di-tert-butyl-p-cresol was not added during the preparation of the functional additive in this comparative example, that is, the functional additive finally prepared in this comparative example does not contain 2,6-di-tert-butyl-p-cresol.

[0045] Performance testing: The inks prepared in Examples 1-3 and Comparative Examples 1-3 were screen-printed onto the surface of the chip. After drying and curing, the printed chip was obtained. The squeegee angle was 65°, the printing speed was 350 mm / s, the screen mesh was 300 mesh, and the screen distance was 3 mm. Then, the following performance tests were performed on each group of samples: 1. High temperature resistance: Place the printed chip at an ambient temperature of 300℃ for 24 hours, then remove it, cool it, and let it stand for 2 hours before observing whether the printed chip has discoloration or cracks.

[0046] 2. Salt spray resistance test: The specific test conditions are as follows: saline concentration 5±1%, pH value 6.5-7.23, air supply pressure 10-25psi, salt spray collection volume 1-2mL / 80cm² / hr, saline tank temperature 5±2℃, and continuous spraying time 48hrs. After the experiment, rinse with distilled water for 5 minutes, air dry, and let stand for 6 hours. Then observe whether the printed chips have discoloration or cracking.

[0047] 3. Ethanol / Butanone Resistance Test: Immerse each group of test samples in ethanol / butanone for 24 hours, then remove them, air dry them, and let them stand for 6 hours. Then observe whether the printed chips have discoloration or cracks.

[0048] 4. Boiling water test: Boil the printed chip in pure water at 100℃ for 30 minutes; after leaving it at room temperature for 2 hours, perform an adhesion test; the specific steps for the adhesion test are as follows: S1. Draw 10×10 small grids of 1mm×1mm on the surface of the printed chip; S2. Clean the sample surface of debris with a lint-free cloth; S3. Apply 3M 610# adhesive tape to the small grid, flatten it, let it stand for 5 seconds, and then quickly pull up the tape. Calculate the area of ​​peeling off. If it exceeds 5%, it is unqualified.

[0049] 5. Pencil Hardness Test: Mitsubishi pencils with a lead hardness ≥3H should be tested at a pressure of 750gf. The lead should be held at a 45° angle to the surface being tested. Five parallel lines, each 10mm long, should be drawn at the test location, with a spacing >3mm between the lines. The test lines should not interfere with each other. Permanent indentations are not allowed on the surface. Minor indentations (0-2mm) at the starting point are permitted, but the surface must function normally. Visible scratches or abrasions are not allowed on other areas.

[0050] 6. Antioxidant Performance: Each group of test samples was placed in a 150℃ forced-air drying oven for accelerated thermal aging for 500 hours. The adhesion grade of the inks before and after aging was tested according to ASTM D3359 standard. Simultaneously, the presence of peeling or cracking was observed in each group of ink samples. A smaller decrease in adhesion grade indicates better antioxidant performance, and thus better antioxidant performance of the ink. Among them, grade 5B means that there is no ink peeling in the gridded area (0% peeling area). Grade 4B indicates minor peeling at the intersections or edges of the grid areas, with the affected area being less than 5%. Grade 3B indicates that there is peeling in the grid area, with an affected area of ​​5% to 15% (some strict scenarios may require ≤10%).

[0051] The test data obtained above are recorded in Tables 1, 2, and 3: Table 1

[0052] Table 2

[0053] Table 3

[0054] By comparing and analyzing the relevant data in the table, it can be seen that the high-durability pad printing ink for special chip marking prepared by this invention not only has excellent high-temperature resistance and chemical resistance, but also good oxidation resistance and scratch resistance. This extends its service life to a certain extent while effectively ensuring its quality. Therefore, this invention provides a high-durability pad printing ink for special chip marking and its preparation method, which has a broader market prospect and is more suitable for widespread application.

[0055] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0056] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high-durability pad printing ink for special chip marking, characterized in that, It is composed of the following raw materials in parts by weight: 10-15 parts polyester resin, 15-20 parts silicone resin, 25-30 parts crosslinking agent, 10-15 parts copper chrome black, 0.8-1.2 parts fumed silica, 5-8 parts functional additives, 1-1.5 parts tetrafluoroethylene wax powder, 15-20 parts isoflurane and 2-4 parts n-butanol.

2. The high-durability pad printing ink for special chip marking according to claim 1, characterized in that, The preparation method of the functional additive includes the following steps: 2,6-di-tert-butyl-p-cresol with a mass of 0.2-0.3 times that of the modified inorganic substrate is added to a DMF dispersion of 10-20 g / L modified inorganic substrate. After uniform dispersion, amino-terminated polydimethylsiloxane, dicyclohexylcarbodiimide, and N-hydroxybenzotriazole with masses of 5-8 times that of the modified inorganic substrate, 1.5-2 times that of the modified inorganic substrate, and 1.2-1.5 times that of the modified inorganic substrate are added respectively. The mixture is reacted at a temperature of 70-80℃ for 5-8 hours under nitrogen protection. The product is then filtered, and the filter cake is washed successively with DMF, distilled water, and ethanol, and then dried under vacuum to obtain the final product. The inorganic substrate is a composite material with spherical cerium oxide as the "core" and nano-zirconia as the "shell".

3. The high-durability pad printing ink for special chip marking according to claim 2, characterized in that, The modified inorganic substrate is prepared as follows: the inorganic substrate is dispersed in an 85-90wt% ethanol aqueous solution at a dosage ratio of 20-50g / L, and 30-50% of the inorganic substrate by mass of 3-aminopropyltriethoxysilane is added. After reflux reaction for 3-5h, the product is filtered, and the resulting filter cake is added to DMF at a mass of 10-15 times its mass. After ultrasonic dispersion for 3-5min, 40-50% of the filter cake by mass of 3-octenyl-2,5-dihydrofurandione is added, and then the reaction is carried out at 40-50℃ for 5-8h. After the reaction is completed, the product is filtered, washed and vacuum dried to obtain the final product.

4. The high-durability pad printing ink for special chip marking according to claim 3, characterized in that, The inorganic substrate is prepared by adding zirconium nitrate and hexamethylenetetramine to an ethanol dispersion of 10-30 g / L spherical cerium oxide, mixing well, and then refluxing and stirring the resulting mixture for 3-5 hours. After the reaction is completed, the product is subjected to solid-liquid separation, washing, drying, and high-temperature calcination treatment to obtain the final product.

5. The high-durability pad printing ink for special chip marking according to claim 4, characterized in that: The concentration of zirconium nitrate in the mixed components is 0.1-0.3 mol / L, and the concentration of hexamethylenetetramine is 1-3 mol / L.

6. The high-durability pad printing ink for special chip marking according to claim 4, characterized in that: The high-temperature calcination temperature is set to 500-700℃, and the high-temperature calcination time is set to 2-4h.

7. The high-durability pad printing ink for special chip marking according to claim 4, characterized in that, The preparation method of spherical cerium oxide is as follows: Cerium nitrate, polyethylene glycol 400 and deionized water are mixed and stirred in a mass ratio of 1:30-35:8-12 until the mixture is clear, and then kept at 160-190℃ for 20-30h. After the reaction is completed, the product is naturally cooled to room temperature, and then filtered, washed, dried and calcined in sequence to obtain the product.

8. The high-durability pad printing ink for special chip marking according to claim 7, characterized in that: The drying temperature is set to 60-80℃, and the drying time is set to 10-15h.

9. The high-durability pad printing ink for special chip marking according to claim 7, characterized in that: The calcination temperature is set to 500-600℃, and the calcination time is set to 2-3h.

10. A method for preparing a high-durability pad printing ink for special chip marking according to any one of claims 1-9, characterized in that, Includes the following steps: Step 1: Weigh each raw material according to the ink formula ratio and put each raw material into a stainless steel kettle. Disperse at high speed at 800-1200r / min for 2-3 hours. The temperature during dispersion should be controlled below 70℃. The second step is to cool the mixture for 24 hours after it is evenly dispersed, and then grind it with a three-roll mill until the fineness is ≤10μm. After grinding, n-butanol is added to adjust the viscosity. The resulting ink has a viscosity of 9000-11000cP at 30℃. The third step is to test the ink obtained in step two. If it passes the test, it will be sealed and packaged to obtain the high-durability pad printing ink for special chip marking.

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