Mold cleaning adhesive for semiconductor packaging mold and preparation method of mold cleaning adhesive

Abstract

The invention relates to the field of semiconductor packaging, in particular to a mold cleaning adhesive for a semiconductor packaging mold and a preparation method of the mold cleaning adhesive. The mold cleaning glue comprises the following components in parts by weight: 15-25 parts of modified organic bentonite, 30-50 parts of nitrile rubber, 5-15 parts of a cleaning agent, 4-10 parts of a surfactant, 3-7 parts of an antioxidant, 2-5 parts of an efficient dispersant and 0.5-2 parts of a cross-linking agent. The modified organobentonite is prepared by performing intercalation modification on organobentonite through a cation-containing solution, performing quaternary ammonium salt cation exchange and reacting with polyethylene glycol diglycidyl ether and triethylene tetramine. The prepared mold cleaning adhesive for the semiconductor packaging mold has excellent cleaning performance and excellent heat resistance and structural strength, and a reliable scheme is provided for cleaning of the semiconductor packaging mold.

Description

Technical Field

[0001] The present invention relates to the technical field of semiconductor packaging mold cleaning, and particularly relates to a mold cleaning adhesive for semiconductor packaging molds and a preparation process thereof. Background Art

[0002] In the field of semiconductor packaging, the cleaning of molds is a key link to ensure product quality and production efficiency. With the continuous progress of semiconductor technology, the packaging process has become increasingly complex, and molds are easily affected by various pollutants during use, such as epoxy resin, curing agent, silicone-based mold release agent, acidic etchant residue, and heavy metal ions. These pollutants not only affect the service life of the molds but also may cause defects in the packaged products, thereby affecting the stability and reliability of the entire production process.

[0003] Traditional mold cleaning methods and mold cleaning adhesives often have difficulty in balancing cleaning effect, convenience, and mold protection when dealing with these complex and diverse pollutants. Existing mold cleaning adhesives have deficiencies in cleaning performance and reusability, and cannot meet the requirements of efficient cleaning. Therefore, developing a new type of mold cleaning adhesive that can effectively remove various pollutants and at the same time has excellent flexibility and high-temperature resistance has become an urgent problem to be solved in the industry. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a mold cleaning adhesive for semiconductor packaging molds and a preparation process thereof, so as to solve the problems that in the semiconductor packaging process, molds are extremely vulnerable to various pollutants, such as epoxy resin, curing agent, silicone-based mold release agent, acidic etchant residue, heavy metal ions, etc., and traditional mold cleaning methods and mold cleaning adhesives are difficult to efficiently deal with these complex and diverse pollutants at the same time, and it is difficult to balance the convenience of the mold cleaning method and the stability of the mold cleaning adhesive while ensuring the cleaning effect.

[0005] Based on the above purpose, the present invention provides a mold cleaning adhesive for semiconductor packaging molds, which is prepared from the following raw materials in parts by weight: modified organic bentonite: 15 - 25 parts, nitrile rubber: 30 - 50 parts, cleaning agent: 5 - 15 parts, surfactant: 4 - 10 parts, antioxidant: 3 - 7 parts, high-efficiency dispersant: 2 - 5 parts, cross-linking agent: 0.5 - 2 parts; The specific preparation method of the modified organic bentonite is as follows: (a) Mix cetyltrimethylammonium bromide and deionized water to prepare a cetyltrimethylammonium bromide solution with a mass fraction of 1%. Add organic bentonite to the solution, stir for 30 - 50 min, then heat to 50 - 70 °C and stir for 1 - 3 h. After filtration, washing, and drying, a crude product is obtained; (b) Add 2-amino-N,N,N-trimethylethane ammonium chloride and 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine into N,N-dimethylformamide, stir for 30 - 50 min, add potassium carbonate, heat up to 80 - 120 °C under stirring, react for 12 - 24 h, cool down to room temperature, add deionized water, and obtain the modified substance after extraction, washing and drying.

[0006] (c) Add the crude product obtained in step (a) into deionized water, stir for 30 - 50 min to obtain a suspension, add the modified substance obtained in step (b) into the suspension, stir and react at room temperature for 8 - 12 h, filter, wash and dry to obtain the modified organic bentonite intermediate.

[0007] (d) Add the modified organic bentonite intermediate obtained in step (c) into dimethyl sulfoxide, stir for 30 - 50 min, then add polyethylene glycol diglycidyl ether and triethylenetetramine, heat up to 90 - 110 °C under stirring, react for 8 - 12 h, cool to room temperature, filter, wash and freeze-dry to obtain the modified organic bentonite.

[0008] Preferably, the cleaning agent refers to one of di-n-butylamine, cyclohexylamine, and triethylenetetramine.

[0009] Preferably, the composite surfactant refers to sodium dodecylbenzenesulfonate or dioctadecyl dimethyl ammonium chloride.

[0010] Preferably, the antioxidant is one of antioxidant 1010, antioxidant 1076, or antioxidant 168.

[0011] Preferably, the high-efficiency dispersant refers to polyvinylpyrrolidone or sodium polyacrylate.

[0012] Preferably, the crosslinking agent refers to benzoyl peroxide or diisopropylbenzene peroxide.

[0013] Preferably, in step (a), the organic bentonite, cetyltrimethylammonium bromide, and deionized water are in a weight ratio of 0.8 - 1.2:0.03 - 0.05:3 - 5.

[0014] Preferably, in step (b), 2-amino-N,N,N-trimethylethane ammonium chloride, 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine, potassium carbonate, N,N-dimethylformamide, and deionized water are in a weight ratio of 0.8 - 1.2:0.8 - 1.2:1.2 - 3:3.2 - 7.2:3.2 - 7.2.

[0015] Preferably, in step (c), the modified substance, the crude product, and deionized water are in a weight ratio of 0.06 - 0.14:0.8 - 1.2:6 - 14.

[0016] Preferably, in step (d), the modified organobentonite intermediate, dimethyl sulfoxide, polyethylene glycol diglycidyl ether and triethylenetetramine are in a weight ratio of 0.8 - 1.2:12 - 28:0.04 - 0.06:0.02 - 0.03.

[0017] Furthermore, the present invention also provides a preparation process for the mold cleaning adhesive for the semiconductor packaging mold, and the specific preparation process is as follows: S1: Add nitrile rubber into a kneader, control the temperature of the kneading chamber at 60 - 80 °C, and plasticize for 5 - 15 min to obtain the plasticized nitrile rubber; S2: Add a high - efficiency dispersant to the plasticized nitrile rubber obtained in step S1, and continue to knead for 3 - 7 min to obtain mixture 1; S3: Add a cleaning agent to mixture 1 obtained in step S2, stir for 5 - 15 min, and then add modified organobentonite, and knead for 10 - 20 min to obtain mixture 2; S4: Add a surfactant, an antioxidant and a cross - linker to mixture 2 obtained in step S3, and knead for 10 - 20 min to obtain a semi - finished mold cleaning adhesive.

[0018] S5: Take out the semi - finished mold cleaning adhesive obtained in step S4 from the kneader, flatten it by a calender and then cut it to obtain a mold cleaning adhesive for a semiconductor packaging mold.

[0019] Advantages of the present invention: 1. The mold cleaning adhesive of the present invention exhibits excellent cleaning performance during the cleaning process of the semiconductor packaging mold. The mold cleaning adhesive has an extremely excellent cleaning effect on various pollutants, can effectively remove common pollutants such as epoxy resin, silicone - containing mold release agent, acidic etching agent and heavy metal ions, and the residue rate is significantly lower than that of traditional mold cleaning materials, ensuring the cleanliness of the mold after use, and thus improving the quality and reliability of the packaged products.

[0020] 2. The mold cleaning adhesive of the present invention shows excellent mechanical strength and heat resistance. The careful design of its raw material formula and preparation process enables a tight and stable cross - linked network structure to be formed among the components, which not only ensures the integrity and service life of the mold cleaning adhesive itself, but also ensures the smooth progress of the mold cleaning operation, avoiding potential impacts on product quality caused by the residue of the mold cleaning adhesive on the mold surface. At the same time, through a unique preparation process of modified organobentonite and the synergistic effect of each component, the mold cleaning adhesive obtains excellent high - temperature resistance. In a high - temperature environment, its structure can remain highly stable, ensuring the high - efficiency and reliability of the mold cleaning operation.

[0021] 3. The mold cleaning adhesive of the present invention has good processing performance. Its raw material formula and preparation process are reasonably designed. During the processing, each component can be evenly mixed and react fully, which is easy to form, effectively reducing the process difficulty and operation complexity in the production process, improving the production efficiency, contributing to large-scale production, and providing strong support for the industrial application of the mold cleaning adhesive for semiconductor packaging molds. Detailed implementation mode

[0022] To make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with specific embodiments.

[0023] Example 1: Preparation of a modified organic bentonite: (a) Mix 9 g of cetyltrimethylammonium bromide and 891 g of deionized water to prepare a 1% cetyltrimethylammonium bromide solution by mass. Add 240 g of organic bentonite to the solution, stir for 30 min, then heat to 50 °C and stir for 1 h. After filtration, washing and drying, a crude product is obtained; (b) Add 20 g of 2-amino-N,N,N-trimethylethanaminium chloride and 20 g of 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine to 80 g of N,N-dimethylformamide, stir for 30 min, add 30 g of potassium carbonate, heat to 80 °C with stirring, react for 12 h, cool to room temperature, add 80 g of deionized water, and obtain a modified substance after extraction, washing and drying.

[0024] (c) Add 200 g of the crude product obtained in step (a) to 1.5 kg of deionized water, stir for 30 min to obtain a suspension. Add 15 g of the modified substance obtained in step (b) to the suspension, stir and react at room temperature for 8 h, then filter, wash and dry to obtain a modified organic bentonite intermediate.

[0025] (d) Add 160 g of the modified organic bentonite intermediate obtained in step (c) to 2.4 kg of dimethyl sulfoxide, stir for 30 min, then add 8 g of polyethylene glycol diglycidyl ether and 4 g of triethylenetetramine, heat to 90 °C with stirring, react for 8 h, cool to room temperature, filter, wash and freeze-dry to obtain the modified organic bentonite.

[0026] The specific preparation process of a mold cleaning adhesive for semiconductor packaging molds is as follows: S1: Add 300 g of nitrile rubber to a kneader, control the temperature of the kneading chamber at 60 °C, and plasticize for 5 min to obtain plasticized nitrile rubber; S2: Add 20 g of polyvinylpyrrolidone to the plasticized nitrile rubber obtained in step S1, and continue to knead for 3 min to obtain mixture 1; S3: Add 50 g of cyclohexylamine to the mixture 1 obtained in step S2, stir for 5 min, then add 150 g of modified organic bentonite, and knead for 10 min to obtain mixture 2; S4: Add 40 g of sodium dodecylbenzenesulfonate, 30 g of antioxidant 1010, and 10 g of benzoyl peroxide to the mixture 2 obtained in step S3, and knead for 10 min to obtain a semi-finished product of mold cleaning rubber.

[0027] S5: Take out the semi-finished product of mold cleaning rubber obtained in step S4 from the internal mixer, flatten it with a calender and then cut it to obtain a mold cleaning rubber for semiconductor packaging molds.

[0028] Example 2: A specific preparation method of modified organic bentonite is as follows: (a) Mix 20 g of cetyltrimethylammonium bromide and 1.98 Kg of deionized water to prepare a 1% cetyltrimethylammonium bromide solution by mass. Add 500 g of organic bentonite to the solution, stir for 40 min, then heat to 60 °C and stir for 2 h. After filtration, washing, and drying, a crude product is obtained; (b) Add 40 g of 2-amino-N,N,N-trimethylethanolammonium chloride and 40 g of 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine to 200 g of N,N-dimethylformamide, stir for 40 min, add 80 g of potassium carbonate, heat to 100 °C with stirring, react for 18 h, cool to room temperature, add 200 g of deionized water, and obtain a modified substance after extraction, washing, and drying.

[0029] (c) Add 400 g of the crude product obtained in step (a) to 4 Kg of deionized water, stir for 40 min to obtain a suspension. Add 40 g of the modified substance obtained in step (b) to the suspension, stir and react at room temperature for 10 h, filter, wash, and dry to obtain a modified organic bentonite intermediate.

[0030] (d) Add 300 g of the modified organic bentonite intermediate obtained in step (c) to 6 Kg of dimethyl sulfoxide, stir for 40 min, then add 15 g of polyethylene glycol diglycidyl ether and 7.5 g of triethylenetetramine, heat to 100 °C with stirring, react for 10 h, cool to room temperature, filter, wash, and freeze-dry to obtain the modified organic bentonite.

[0031] A specific preparation process of a mold cleaning rubber for semiconductor packaging molds is as follows: S1: Add 400 g of nitrile rubber to an internal mixer, control the temperature of the mixing chamber at 70 °C, and plasticate for 10 min to obtain plasticated nitrile rubber; S2: Add 35 g of polyvinylpyrrolidone to the plasticated nitrile rubber obtained in step S1, and continue to knead for 5 min to obtain mixture 1; S3: Add 100 g of cyclohexylamine to the mixture 1 obtained in step S2, stir for 10 min, then add 200 g of modified organobentonite, and knead for 15 min to obtain mixture 2; S4: Add 70 g of sodium dodecylbenzenesulfonate, 50 g of antioxidant 1010, and 20 g of benzoyl peroxide to the mixture 2 obtained in step S3, and knead for 15 min to obtain the semi-finished product of the mold cleaning rubber.

[0032] S5: Take out the semi-finished product of the mold cleaning rubber obtained in step S4 from the internal mixer, flatten it with a calender and then cut it to obtain a mold cleaning rubber for semiconductor packaging molds.

[0033] Example 3: Preparation of a modified organobentonite: (a) Mix 15 g of cetyltrimethylammonium bromide and 1.485 Kg of deionized water to prepare a 1% cetyltrimethylammonium bromide solution by mass. Add 360 g of organobentonite to the solution, stir for 50 min, then heat to 70 °C and stir for 3 h. After filtration, washing, and drying, a crude product is obtained; (b) Add 40 g of 2-amino-N,N,N-trimethylethanolammonium chloride and 40 g of 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine to 240 g of N,N-dimethylformamide, stir for 50 min, add 100 g of potassium carbonate, heat to 120 °C with stirring, react for 24 h, cool to room temperature, add 240 g of deionized water, and obtain a modified substance after extraction, washing, and drying.

[0034] (c) Add 360 g of the crude product obtained in step (a) to 4.2 Kg of deionized water, stir for 50 min to obtain a suspension. Add 42 g of the modified substance obtained in step (b) to the suspension, stir and react at room temperature for 12 h, filter, wash, and dry to obtain a modified organobentonite intermediate.

[0035] (d) Add 360 g of the modified organobentonite intermediate obtained in step (c) to 8.4 Kg of dimethyl sulfoxide, stir for 50 min, then add 18 g of polyethylene glycol diglycidyl ether and 9 g of triethylenetetramine, heat to 110 °C with stirring, react for 12 h, cool to room temperature, filter, wash, and freeze-dry to obtain the modified organobentonite.

[0036] The specific preparation process of a mold cleaning rubber for semiconductor packaging molds is as follows: S1: Add 500 g of nitrile rubber to an internal mixer, control the temperature of the mixing chamber at 80 °C, and plasticize for 15 min to obtain the plasticized nitrile rubber; S2: Add 50 g of polyvinylpyrrolidone to the plasticized nitrile rubber obtained in step S1, and continue to knead for 7 min to obtain mixture 1; S3: Add 150 g of cyclohexylamine to the mixture 1 obtained in step S2, stir for 15 min, then add 250 g of modified organic bentonite, and knead for 20 min to obtain mixture 2; S4: Add 100 g of sodium dodecylbenzenesulfonate, 70 g of antioxidant 1010, and 30 g of benzoyl peroxide to the mixture 2 obtained in step S3, and knead for 20 min to obtain a semifinished product of mold cleaning rubber.

[0037] S5: Take out the semifinished product of mold cleaning rubber obtained in step S4 from the internal mixer, flatten it with a calender and then cut it to obtain a mold cleaning rubber for semiconductor packaging molds.

[0038] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine is replaced by p-chlorobenzylamine. The specific preparation method of a modified organic bentonite is as follows: (a) Mix 20 g of cetyltrimethylammonium bromide and 1.98 Kg of deionized water to prepare a 1% cetyltrimethylammonium bromide solution by mass. Add 500 g of organic bentonite to the solution, stir for 40 min, then heat up to 60 °C and stir for 2 h. After filtration, washing, and drying, a crude product is obtained; (b) Add 40 g of 2-amino-N,N,N-trimethylethanaminium chloride and 40 g of p-chlorobenzylamine to 200 g of N,N-dimethylformamide, stir for 40 min, add 80 g of potassium carbonate, heat up to 100 °C with stirring, react for 18 h, cool down to room temperature, add 200 g of deionized water, and after extraction, washing, and drying, a 2-amino-N,N,N-trimethylethanaminium chloride derivative containing a benzylamino structure is obtained.

[0039] (c) Add 400 g of the crude product obtained in step (a) to 4 Kg of deionized water, stir for 40 min to obtain a suspension. Add 40 g of the 2-amino-N,N,N-trimethylethanaminium chloride derivative containing a benzylamino group obtained in step (b) to the suspension, stir and react at room temperature for 10 h, filter, wash, and dry to obtain a modified organic bentonite intermediate.

[0040] (d) Add 300 g of the modified organic bentonite intermediate obtained in step (c) to 6 Kg of dimethyl sulfoxide, stir for 40 min, then add 15 g of polyethylene glycol diglycidyl ether and 7.5 g of triethylenetetramine, heat up to 100 °C with stirring, react for 10 h, cool down to room temperature, filter, wash, and freeze-dry to obtain the modified organic bentonite.

[0041] The specific preparation process of a mold cleaning rubber for semiconductor packaging molds is as follows: S1: Add 400 g of nitrile rubber into a Banbury mixer, control the temperature of the mixing chamber at 70 °C, and plastify for 10 min to obtain the plastified nitrile rubber; S2: Add 35 g of polyvinylpyrrolidone to the plastified nitrile rubber obtained in step S1, and continue mixing for 5 min to obtain mixture 1; S3: Add 100 g of cyclohexylamine to mixture 1 obtained in step S2, stir for 10 min, then add 200 g of modified organic bentonite, and mix for 15 min to obtain mixture 2; S4: Add 70 g of sodium dodecylbenzenesulfonate, 50 g of antioxidant 1010, and 20 g of benzoyl peroxide to mixture 2 obtained in step S3, and mix for 15 min to obtain the semi-finished product of the mold cleaning rubber.

[0042] S5: Take out the semi-finished product of the mold cleaning rubber obtained in step S4 from the Banbury mixer, flatten it by a calender and then cut it to obtain a mold cleaning rubber for semiconductor packaging molds.

[0043] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine is not added. The specific steps are as follows: Preparation of a modified organic bentonite: (a) Mix 20 g of cetyltrimethylammonium bromide and 1.98 Kg of deionized water to prepare a 1% cetyltrimethylammonium bromide solution by mass. Add 500 g of organic bentonite to the solution, stir for 40 min, then heat to 60 °C and stir for 2 h. After filtration, washing, and drying, a crude product is obtained; (b) Add 400 g of the crude product obtained in step (a) to 4 Kg of deionized water, stir for 40 min to obtain a suspension. Add 40 g of 2-amino-N,N,N-trimethylethanolammonium chloride to the suspension, stir and react at room temperature for 10 h, filter, wash, and dry to obtain an organic bentonite with amino intercalation modification.

[0044] (c) Add 300 g of the organic bentonite with amino intercalation modification obtained in step (b) to 6 Kg of dimethyl sulfoxide, stir for 40 min, then add 15 g of polyethylene glycol diglycidyl ether and 7.5 g of triethylenetetramine. Stir and heat to 100 °C, react for 10 h, cool to room temperature, filter, wash, and freeze-dry to obtain the modified organic bentonite.

[0045] The specific preparation process of a mold cleaning rubber for semiconductor packaging molds is as follows: S1: Add 400 g of nitrile rubber into a Banbury mixer, control the temperature of the mixing chamber at 70 °C, and plastify for 10 min to obtain the plastified nitrile rubber; S2: Add 35 g of polyvinylpyrrolidone to the plastified nitrile rubber obtained in step S1, and continue mixing for 5 min to obtain mixture 1; S3: Add 100 g of cyclohexylamine to the mixture 1 obtained in step S2, stir for 10 min, then add 200 g of modified organic bentonite, and knead for 15 min to obtain mixture 2; S4: Add 70 g of sodium dodecylbenzenesulfonate, 50 g of antioxidant 1010, and 20 g of benzoyl peroxide to the mixture 2 obtained in step S3, and knead for 15 min to obtain the semifinished product of mold cleaning rubber.

[0046] S5: Take out the semifinished product of mold cleaning rubber obtained in step S4 from the internal mixer, flatten it by a calender and then cut it to obtain a mold cleaning rubber for semiconductor packaging molds.

[0047] Comparative example 3: The difference between comparative example 3 and example 2 is that the modified organic bentonite is replaced by organic bentonite. The specific preparation process of a mold cleaning rubber for semiconductor packaging molds is as follows: S1: Add 400 g of nitrile rubber to the internal mixer, control the temperature of the internal mixer chamber at 70 °C, and plasticize for 10 min to obtain the plasticized nitrile rubber; S2: Add 35 g of polyvinylpyrrolidone to the plasticized nitrile rubber obtained in step S1, and continue to knead for 5 min to obtain mixture 1; S3: Add 100 g of cyclohexylamine to the mixture 1 obtained in step S2, stir for 10 min, then add 200 g of organic bentonite, and knead for 15 min to obtain mixture 2; S4: Add 70 g of sodium dodecylbenzenesulfonate, 50 g of antioxidant 1010, and 20 g of benzoyl peroxide to the mixture 2 obtained in step S3, and knead for 15 min to obtain the semifinished product of mold cleaning rubber.

[0048] S5: Take out the semifinished product of mold cleaning rubber obtained in step S4 from the internal mixer, flatten it by a calender and then cut it to obtain a mold cleaning rubber for semiconductor packaging molds.

[0049] Comparative example 4: The difference between comparative example 4 and example 2 is that triethylenetetramine is not added. The specific steps are as follows: Preparation of a modified organic bentonite: (a) Mix 20 g of cetyltrimethylammonium bromide and 1.98 Kg of deionized water to prepare a 1% cetyltrimethylammonium bromide solution by mass. Add 500 g of organic bentonite to the solution, stir for 40 min, then heat up to 60 °C and stir for 2 h. After filtration, washing, and drying, a crude product is obtained; (b) Add 40 g of 2-amino-N,N,N-trimethylammonium chloride and 40 g of 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine to 200 g of N,N-dimethylformamide, stir for 40 min, add 80 g of potassium carbonate, heat to 100 °C with stirring, react for 18 h, cool to room temperature, add 200 g of deionized water, and obtain the modified substance after extraction, washing, and drying.

[0050] (c) Add 400 g of the crude product obtained in step (a) to 4 Kg of deionized water, stir for 40 min to obtain a suspension, add 40 g of the modified substance obtained in step (b) to the suspension, stir and react at room temperature for 10 h, filter, wash, and dry to obtain the modified organobentonite intermediate.

[0051] (d) Add 300 g of the modified organobentonite intermediate obtained in step (c) to 6 Kg of dimethyl sulfoxide, stir for 40 min, then add 15 g of polyethylene glycol diglycidyl ether, heat to 100 °C with stirring, react for 10 h, cool to room temperature, filter, wash, and freeze-dry to obtain the modified organobentonite.

[0052] The specific preparation process of a mold cleaning adhesive for semiconductor packaging molds is as follows: S1: Add 400 g of nitrile rubber to a kneader, control the temperature of the kneading chamber at 70 °C, and plastify for 10 min to obtain the plastified nitrile rubber. S2: Add 35 g of polyvinylpyrrolidone to the plastified nitrile rubber obtained in step S1, and continue to knead for 5 min to obtain mixture 1. S3: Add 100 g of cyclohexylamine to mixture 1 obtained in step S2, stir for 10 min, then add 200 g of modified organobentonite, and knead for 15 min to obtain mixture 2. S4: Add 70 g of sodium dodecylbenzenesulfonate, 50 g of antioxidant 1010, and 20 g of benzoyl peroxide to mixture 2 obtained in step S3, and knead for 15 min to obtain the semi-finished mold cleaning adhesive.

[0053] S5: Take out the semi-finished mold cleaning adhesive obtained in step S4 from the kneader, flatten it by a calender and then cut it to obtain a mold cleaning adhesive for semiconductor packaging molds.

[0054] Performance test Mold cleaning effect test: To achieve the accuracy and standardization of the amount of pollutants in semiconductor packaging molds, the following operations can be carried out: Prepare six semiconductor packaging molds of the same model without contamination, simulate pollutants by the following methods to make the contamination degree of each pollutant on the mold surface highly standardized: For the silicon-containing mold release agent, weigh 0.50 g using an electronic balance with a precision of 0.01 mg, dissolve it in 10 g of toluene, stir well, and then use a pipette to take 0.5 g of this solution and evenly apply it to an area of 100 cm² on the mold surface.

[0055] For the acidic etchant, select the common hydrofluoric acid-nitric acid mixed etchant, prepare 5 g of the etchant solution according to a weight ratio of 1:3, where the concentration of hydrofluoric acid is 5% and the concentration of nitric acid is 15%. Use a spray gun to evenly spray the solution on the above 100 cm² area at a flow rate of 0.5 g / min.

[0056] For the copper sulfate solution simulating copper ion pollution, prepare 10 g of a copper sulfate solution with a concentration of 6.4 g / kg, take 1 g of this solution, and evenly drip it on the same 100 cm² area of the mold.

[0057] For the epoxy resin, weigh 1.00 g of bisphenol A epoxy resin, add 0.1 g of curing agent, mix well, and then apply and cure an epoxy resin layer with a thickness of about 0.5 mm on the above 100 cm² area.

[0058] Use the mold cleaning adhesives of Examples 1-3 and Comparative Examples 1-3 for mold cleaning operations respectively. Evenly apply the mold cleaning adhesive on the above 100 cm² area with a thickness of 2 mm. The mold cleaning conditions are a temperature of 200 °C, a pressure of 12 MPa, and a time of 25 min. The residual rates of various pollutants after mold cleaning are shown in Table 1.

[0059] Tensile strength and elongation at break test: Use a universal material testing machine to conduct tensile tests on the mold cleaning adhesives prepared in the examples and comparative examples to obtain the tensile strength and elongation at break of the mold cleaning adhesives. The clamp spacing is 20 mm, the tensile rate is 20 mm / min, each group is tested 3 times, and the average value is taken. The test results are shown in Table 1.

[0060] High temperature resistance test: Use a thermogravimetric analyzer to test the experimental materials at a heating rate of 10 °C / min in a nitrogen atmosphere, record the thermal decomposition temperature, each group is tested three times, and the average value is taken. The test results are shown in Table 1.

[0061] Table 1 Performance test results

[0062] Data analysis: It can be seen from Examples 1-3 in Table 1 that the mold cleaning adhesive prepared by the mold cleaning adhesive preparation method for semiconductor packaging molds of the present invention has extremely strong cleaning effects on the silicon-containing mold release agent, acidic etchant, copper ions, and epoxy resin contained in the pollutants of the packaging mold, and has improvements in mechanical properties and heat resistance.

[0063] As can be seen from Example 2 and Comparative Example 1 in Table 1, the mold cleaning adhesive for semiconductor packaging molds prepared with the modified organic bentonite utilized in the present invention has a very good cleaning effect. This may be because in terms of adsorption, 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine can enter the interlayer of the organic bentonite, further increasing the layer spacing and providing more adsorption space; in terms of mechanical properties and heat resistance, compared with a single benzene ring structure, it is more effective in increasing the molecular rigidity and steric hindrance, making the arrangement between molecular chains more compact and orderly, thereby improving the structural strength. In a high-temperature environment, it can serve as a stable structural unit, slowing down the thermal movement and degradation rate of molecules.

[0064] As can be seen from Example 2 and Comparative Example 2 in Table 1, for the mold cleaning adhesive for semiconductor packaging molds prepared with unmodified organic bentonite without adding 7-chloro-1,2,3,4-tetrahydronaphthalen-1-amine, all data are lower compared to Example 2. This may be because the lack of a cyclic structure reduces the hydrophobic property of the organic bentonite. When removing organic pollutants such as silicone-based release agents, the hydrophobic property of the mold cleaning adhesive molecules decreases, weakening the affinity with organic pollutants; at the same time, due to the lack of the introduction of a cyclic rigid structure, under high temperature and high pressure, there is no good support between the interlayers of the organic bentonite, and intermolecular collapse and slippage are likely to occur, thus reducing the overall mechanical properties and heat resistance of the mold cleaning adhesive.

[0065] As can be seen from Example 2 and Comparative Example 3 in Table 1, for the mold cleaning adhesive for semiconductor packaging molds prepared with unmodified organic bentonite, all its properties are far inferior to those of Example 2. In terms of adsorption capacity, this may be because the surface property of unmodified organic bentonite is hydrophilic and oleophobic, with a very weak adsorption force for organic pollutants, and at the same time, without the introduction of specific groups, it cannot efficiently adsorb certain special pollutants. In terms of mechanical strength and heat resistance, due to the lack of rigid groups and cross-linked structures, the intermolecular force is weak. When subjected to external forces, such as friction and stretching during the mold cleaning process, the molecular chains are prone to slippage and fracture, significantly reducing the mechanical strength of the mold cleaning adhesive.

[0066] As can be seen from Example 2 and Comparative Example 4 in Table 1, triethylenetetramine is crucial in the process of modifying organic bentonite. This may be because triethylenetetramine contains multiple amino groups, and these amino groups can significantly increase the adsorption sites for acidic substances and metal ion pollutants. At the same time, it strengthens the cross-linked network formed by polyethylene glycol diglycidyl ether and the modified substance, like "lock catches" firmly fixing the cross-linked structure, enhancing the overall strength and stability of the material. This strengthened cross-linked structure can effectively prevent problems such as interlayer structure collapse and component shedding of the organic bentonite under high-temperature and high-pressure conditions during the mold cleaning process, maintaining the integrity and performance stability of the mold cleaning adhesive.

[0067] Those of ordinary skill in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the present invention is limited to these examples; under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, which are not provided in detail for the sake of brevity.

Claims

1. A mold cleaning adhesive for semiconductor packaging molds, characterized in that It includes the following raw materials in parts by weight: modified organic bentonite: 15 - 25 parts, nitrile rubber: 30 - 50 parts, cleaning agent: 5 - 15 parts, surfactant: 4 - 10 parts, antioxidant: 3 - 7 parts, high - efficiency dispersant: 2 - 5 parts, cross - linker: 0.5 - 2 parts; The specific preparation method of the said modified organic bentonite is as follows: (a) Mix organic bentonite, cetyltrimethylammonium bromide and deionized water, keep stirring at 50 - 70 °C for 1 - 3 h, filter, wash and dry to obtain the crude product; (b) Mix 2 - amino - N,N,N - trimethylethane ammonium chloride, 7 - chloro - 1,2,3,4 - tetrahydronaphthalen - 1 - amine, potassium carbonate and N,N - dimethylformamide, heat up to 80 - 120 °C, stir and react for 12 - 24 h, cool down to room temperature, add deionized water, extract, wash and dry to obtain the modified substance; (c) Add the modified substance obtained in step (b) and the crude product obtained in step (a) into deionized water, stir and react at room temperature for 8 - 12 h, filter, wash and dry to obtain the modified organic bentonite intermediate; (d) Add the modified organic bentonite intermediate obtained in step (c), polyethylene glycol diglycidyl ether and triethylenetetramine into dimethyl sulfoxide, stir and heat up to 90 - 110 °C, react for 8 - 12 h, cool down to room temperature, filter, wash and freeze - dry to obtain the modified organic bentonite.

2. The mold cleaning adhesive for semiconductor packaging molds according to claim 1, wherein The said cleaning agent refers to one of di - n - butylamine, cyclohexylamine and triethylenetetramine.

3. The mold cleaning adhesive for semiconductor packaging molds according to claim 1, wherein The said surfactant refers to sodium dodecylbenzenesulfonate or dioctadecyl dimethyl ammonium chloride.

4. The mold cleaning adhesive for semiconductor packaging molds according to claim 1, wherein The said antioxidant is one of antioxidant 1010, antioxidant 1076 or antioxidant 168.

5. The mold cleaning adhesive for semiconductor packaging molds according to claim 1, wherein The said high - efficiency dispersant refers to polyvinylpyrrolidone or sodium polyacrylate, and the cross - linker refers to benzoyl peroxide or dicumyl peroxide.

6. The mold cleaning adhesive for semiconductor packaging molds according to claim 1, wherein In the said step (a), the weight ratio of organic bentonite, cetyltrimethylammonium bromide and deionized water is 0.8 - 1.2:0.03 - 0.05:3 - 5.

7. The mold cleaning adhesive for semiconductor packaging molds according to claim 1, characterized in that In the said step (b), the weight ratio of 2 - amino - N,N,N - trimethylethane ammonium chloride, 7 - chloro - 1,2,3,4 - tetrahydronaphthalen - 1 - amine, potassium carbonate, N,N - dimethylformamide and deionized water is 0.8 - 1.2:0.8 - 1.2:1.2 - 3:3.2 - 7.2:3.2 - 7.

2.

8. The mold cleaning adhesive for semiconductor packaging molds according to claim 1, wherein, In the said step (c), the weight ratio of the modified substance, the crude product and deionized water is 0.06 - 0.14:0.8 - 1.2:6 - 14.

9. The mold cleaning adhesive for semiconductor packaging molds according to claim 1, wherein In the said step (d), the weight ratio of the modified organic bentonite intermediate, dimethyl sulfoxide, polyethylene glycol diglycidyl ether and triethylenetetramine is 0.8 - 1.2:12 - 28:0.04 - 0.06:0.02 - 0.

03.

10. A preparation method of a mold cleaning adhesive for a semiconductor packaging mold according to any one of claims 1-9, characterized in that, It includes the following steps: S1: Add nitrile rubber into an internal mixer, control the temperature of the mixing chamber at 60 - 80 °C, plastify for 5 - 15 min to obtain the plastified nitrile rubber; S2: Add the high - efficiency dispersant onto the plastified nitrile rubber obtained in step S1, continue to mix for 3 - 7 min to obtain mixture 1; S3: Add the cleaning agent and modified organic bentonite into the mixture 1 obtained in step S2, and knead for 10 - 20 min to obtain mixture 2; S4: Add the surfactant, antioxidant and crosslinking agent into the mixture 2 obtained in step S3, and knead for 10 - 20 min to obtain the semi-finished product of the mold cleaning rubber; S5: Take out the semi-finished product of the mold cleaning rubber obtained in step S4 from the internal mixer, flatten it through a calender and then cut it to obtain a mold cleaning rubber for semiconductor packaging molds.

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