Scale dissolving glue as well as preparation method and application thereof

Abstract

The invention relates to the technical field of rubber, in particular to scale-dissolving rubber as well as a preparation method and application thereof. The rubber composition comprises the following components in parts by weight: 100 parts of unvulcanized rubber, 40-70 parts of a reinforcing filler, 5-30 parts of a cleaning agent, 7-20 parts of a surfactant, 1-5 parts of a vulcanizing agent and 5-30 parts of an auxiliary agent, the surface active agent comprises alkyl ethoxy polyglycosides, the cleaning efficiency of the semiconductor mold can be improved, and the mold cleaning effect can reach 90% through two times of scale glue removal and two times of adhesive removal; by limiting the use amount of the surfactant to be 10-20 parts, the cleaning efficiency of the semiconductor mold can be further improved, and the mold cleaning effect can reach 100% through two times of scale glue dissolving and two times of glue sticking and removing.

Description

Technical Field

[0001] The present invention relates to the field of rubber technology, and in particular to a scale-removing glue and a preparation method and application thereof. Background Art

[0002] In today's era of rapid technological advancement, the semiconductor packaging industry, a crucial sector, is experiencing unprecedented growth. Within this process, mold cleaning has become crucial for ensuring packaging quality. However, the complexity of semiconductor products and the stringent nature of the packaging process place higher demands on mold cleanliness, especially in large-scale production environments with stringent quality control. While widely used for their low cost, ease of use, and environmental friendliness, conventional mold cleaning rubbers are inadequate for cleaning difficult-to-remove mold contaminants. These contaminants often consist of resin residue and organic oxides generated at high temperatures. These contaminants are not only thick but also form strong interfacial bonds with the mold cleaning rubber, making them difficult to completely remove. This not only affects the performance of the packaging material but can also lead to quality issues during production, severely impacting the efficiency of the entire supply chain.

[0003] Chinese invention patent application CN115975274A discloses a mold cleaning adhesive for cleaning rubber molds. This adhesive is used for cleaning rubber molds and is composed of the following components by weight: 30.0-65.0% raw rubber; 12.5-41.0% reinforcing agent; 0.5-3.0% active agent; 2.5-8.5% tackifier; 1.0-5.0% penetrant; 2.5-10.5% cleaning agent; and 0.3-2.0% vulcanizing agent. This mold cleaning adhesive has complex ingredients, high cost, and a complex preparation process requiring a second mixing step, resulting in low production efficiency. When used in semiconductor packaging molds, it suffers from low cleaning efficiency and poor mold cleaning results, making it difficult to meet the needs of large-volume customers. Summary of the Invention

[0004] The first aspect of the present invention provides a scale-removing glue, which comprises, by weight, 100 parts of unvulcanized rubber, 40-70 parts of reinforcing filler, 5-30 parts of cleaning agent, 7-20 parts of surfactant, 1-5 parts of vulcanizing agent, and 5-30 parts of auxiliary agent; the surfactant comprises alcohol ether glycoside (AEG). Optionally, the amount of the surfactant is 10-20 parts.

[0005] Optionally, the amount of the surfactant is 15-20 parts.

[0006] Optionally, the amount of the surfactant is 20 parts.

[0007] The content of glycoside in the alcohol ether glycoside is 60-75 wt %.

[0008] Optionally, the content of glycoside in the alcohol ether glycoside is 65-75 wt%.

[0009] Optionally, the content of glycoside in the alcohol ether glycoside is 70 wt%.

[0010] Optionally, the brand of the alcohol ether glycoside is AEG300.

[0011] Research in this application has found that a descaling adhesive, comprising, by weight, 100 parts unvulcanized rubber, 40-70 parts reinforcing filler, 5-30 parts cleaning agent, 7-20 parts surfactant, 1-5 parts vulcanizing agent, and 5-30 parts additives, can improve the cleaning efficiency of semiconductor molds. After two applications of the descaling adhesive and two applications of adhesive descaling, mold cleaning efficiency can reach 90%. This is likely due to the fact that AEG reduces interfacial tension and enhances permeability while its hydrophobic alkyl chains intercalate into contaminants, disrupting intermolecular forces and loosening hard residues. Furthermore, the polyoxyethylene (EO) chains and glucosides synergistically encapsulate oil molecules, forming an O / W microemulsion and preventing secondary deposition. Further research has found that limiting the surfactant dosage to 10-20 parts further improves semiconductor mold cleaning efficiency, achieving 100% mold cleaning efficiency after two applications of the descaling adhesive and two applications of adhesive descaling. It is possible that AEG with a specific glycoside content forms a water molecule bridging network, which enhances the capillary force on the nanogaps, thereby achieving precise control of wetting permeability and molecular conformation, matching the size of semiconductor pollutants.

[0012] The surfactant in the descaling glue is released through molding and precipitated onto the mold surface, working in conjunction with other cleaning agents in the rubber formula to clean the mold. By limiting the weight ratio of unvulcanized rubber to reinforcing filler to 1: (0.4-0.6), the stability of the mold cleaning can be further improved. This may be due to a balance between the precipitation ability and precipitation speed of the mold cleaning agents. If the surfactant precipitates too quickly, it may inhibit the sufficient precipitation of other mold cleaning agents; if the surfactant precipitates too slowly, it will be difficult to fully infiltrate and spread the mold surface, thus failing to achieve the design purpose. At the same time, because the use environment of the descaling glue of this application involves cleaning semiconductor molds in a high-temperature environment, there is a problem of high-temperature stability. The applicant further discovered that by limiting the weight ratio of cleaning agent to surfactant to (7-13): (10-20), the cleaning performance of the descaling glue at high temperatures can be improved to meet the cleaning operation of semiconductor molds, which may be a balance between cleanability and mechanical properties.

[0013] The weight ratio of the unvulcanized rubber to the reinforcing filler is 1:(0.4-0.6).

[0014] The weight ratio of the cleaning agent to the surfactant is (7-13): (10-20).

[0015] Optionally, the weight ratio of the cleaning agent to the surfactant is 1:(1-2).

[0016] Optionally, the amount of the surfactant is 10-20 parts.

[0017] The unvulcanized rubber includes at least one of butyl rubber, chloroprene rubber, hydrogenated nitrile rubber, natural rubber, fluororubber, silicone rubber, styrene-butadiene rubber, EPDM rubber, and butadiene rubber.

[0018] The reinforcing filler includes at least one of white carbon black, nano calcium carbonate, carbon black, diatomaceous earth, talc powder, mica powder and montmorillonite.

[0019] The cleaning agent includes at least one of ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, hydroxyethylethylenediamine, methyl isobutyl ketone, ethyl isobutyl ketone, methyl ethyl ketone, acetone, butanone, cyclohexane, propylene oxide, methyl acetate, ethyl acetate, and propyl acetate.

[0020] The vulcanizing agent includes at least one of bis-2,5-di-tert-butylperoxy)hexane, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butylperoxyisopropylbenzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, dicyclohexyl peroxydicarbonate, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0021] The auxiliary agent includes at least one of a cleaning auxiliary agent, a vulcanizing auxiliary agent, a processing auxiliary agent and a dye.

[0022] Optionally, the processing aid includes at least one of paraffin wax, stearic acid, polyethylene wax, and zinc stearate.

[0023] Optionally, the cleaning aid includes at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, and barium hydroxide.

[0024] Optionally, the vulcanization aid includes at least one of dibenzothiazyl disulfide, tetramethylthiuram disulfide, and N-tert-butyl-2-benzothiazole sulfenamide.

[0025] The second aspect of the present invention provides a method for preparing a scale-removing rubber, comprising the following steps: plasticizing unvulcanized rubber; sequentially adding a reinforcing filler, a cleaning agent, a surfactant, an auxiliary agent and a vulcanizing agent, and mixing to obtain a mixed rubber; and molding the mixed rubber to obtain the scale-removing rubber.

[0026] Optionally, the mixing temperature is 70-150° C. and the mixing time is 10-60 min.

[0027] Optionally, the mixing temperature is 80-110° C. and the mixing time is 15-30 min.

[0028] A third aspect of the present invention provides an application of a descaling glue for use in cleaning semiconductor molds. Beneficial effects 1. The descaling glue comprises the following components by weight: 100 parts of unvulcanized rubber, 40-70 parts of reinforcing filler, 5-30 parts of cleaning agent, 7-20 parts of surfactant, 1-5 parts of vulcanizing agent, and 5-30 parts of auxiliary agent; the surfactant includes alcohol ether glycoside, which can improve the cleaning efficiency of semiconductor molds. After two applications of descaling glue and two applications of adhesive removal and cleaning, the mold cleaning effect can reach 90%.

[0029] 2. By limiting the amount of surfactant to 10-20 parts, and the surfactant is an alcohol ether glycoside, and the glycoside content in the alcohol ether glycoside is 60-75wt%, the cleaning efficiency of the semiconductor mold can be further improved. After two times of descaling glue and two times of adhesive removal cleaning, the mold cleaning effect can reach 100%.

[0030] 3. By limiting the weight ratio of unvulcanized rubber to reinforcing filler to 1: (0.4-0.6), the stability of mold cleaning can be further improved.

[0031] 4. By limiting the weight ratio of cleaning agent to surfactant to (7-13): (10-20), the cleaning performance of the descaling glue at high temperature can be improved to meet the cleaning requirements of semiconductor molds.

[0032] 5. The scale-removing glue prepared in this application only requires single mixing, and has high production efficiency. DETAILED DESCRIPTION

[0033] Examples 1-3, Comparative Examples 1-11 A scale-removing gel, the components of which are shown in Table 1 in parts by weight: Table 1 Components Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Unvulcanized rubber 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Reinforcing fillers 50 50 50 50 50 50 50 50 50 50 50 50 50 50 cleaning agent 10 10 10 20 10 10 10 10 10 10 10 10 10 10 Surfactant 1 10 15 20 0 0 1 3 5 7 9 25 0 0 0 Surfactant 2 0 0 0 0 0 0 0 0 0 0 0 20 0 0 Surfactant 3 0 0 0 0 0 0 0 0 0 0 0 0 20 0 Surfactant 4 0 0 0 0 0 0 0 0 0 0 0 0 0 20 Surfactant 5 0 0 0 0 10 0 0 0 0 0 0 0 0 0 vulcanizing agent 3 3 3 3 3 3 3 3 3 3 3 3 3 3 additives 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Among them, the component information in Table 1 is as follows: Unvulcanized rubber: EPDM, purchased from Daqing Petrochemical EPDM 4045M; Reinforcing filler: white carbon black, purchased from Zhongbei Fine Chemicals-ZB-2000; Cleaning agent: ethanolamine, purchased from Sichuan Fine Chemical Research and Design Institute Co., Ltd.; Surfactant 1: alcohol ether glycoside AEG300, glycoside content 70 wt%, purchased from Jiangsu Wanqi Biotechnology Co., Ltd.; Surfactant 2: alcohol ether glycoside AEG808Y, glycoside content of about 80 wt%, purchased from Jiangsu Wanqi Biotechnology Co., Ltd.; Surfactant 3: alcohol ether glycoside AE808YB3, glycoside content of about 80 wt%, purchased from Jiangsu Wanqi Biotechnology Co., Ltd.; Surfactant 4: alcohol ether glycoside AEG8108Y, glycoside content of about 81 wt%, purchased from Jiangsu Wanqi Biotechnology Co., Ltd.; Surfactant 5: NP-10, purchased from Foshan Xilong Chemical Co., Ltd.; Curing agent: di-tert-butyl peroxyisopropylbenzene; Additives (processing aids): stearic acid, purchased from Aladdin Chemical; A method for preparing a scale-removing rubber comprises the following steps: plasticizing unvulcanized rubber for 3 minutes, sequentially adding a reinforcing filler, a cleaning agent, a surfactant, and an auxiliary agent, and finally adding a vulcanizing agent; kneading the rubber for 25 minutes under the condition of controlling the temperature at 95°C to obtain a uniform mixed rubber; and then molding the mixed rubber using a molding machine to obtain the scale-removing rubber.

[0034] Performance testing methods The descaling glues in the examples and comparative examples were tested for mold cleaning performance. The test data are listed in Table 2. The cleaning performance was calculated based on the area of mold contamination removed. That is, the data in Table 2 were obtained by the following calculation: (area of mold contamination removed / area of original mold contamination) × 100%. "-" means that the test was not performed.

[0035] Cleaning includes descaling, removing glue and cleaning the mold, and removing glue and cleaning the mold.

[0036] Cleaning mold with descaling glue: Place descaling glue on the mold surface and perform mold cleaning twice in sequence, corresponding to A1 and A2 respectively.

[0037] Adhesive remover and mold cleaning: Place the adhesive remover on the mold surface and press-clean the mold 2-4 times in sequence, corresponding to B1-B4 respectively.

[0038] Evaluation criteria: 100% removal of mold contamination is considered OK; otherwise, it is considered NG.

[0039] Among them, Examples 1-3 and Comparative Examples 2-11 were sequentially subjected to two times of descaling glue mold cleaning (A1 and A2) and two times of adhesive glue mold cleaning (B1 and B2); Comparative Example 1 was not subjected to descaling glue mold cleaning, and only four times of adhesive glue mold cleaning (B1, B2, B3 and B4) were performed; the adhesive glue was selected from the 6# glue described in Example 6 of the Chinese invention patent CN107011553A; the cleaned mold was a machine after 5 days of operation at the client, with a total packaging mold count of 500 molds, and only adhesive glue cleaning was used during the operation period.

[0040] Performance test data Table 2 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 A1 5 5 5 - 5 5 5 5 5 5 5 5 5 5 A2 10 10 10 - 10 5 10 10 10 10 10 10 10 10 B1 80 80 90 20 60 30 90 60 90 95 60 50 60 50 B2 100 100 100 50 70 60 70 80 90 90 70 70 70 70 B3 - - - 70 - - - - - - - - - - B4 - - - 85 - - - - - - - - - - evaluate OK OK OK NG NG NG NG NG NG NG NG NG NG NG As shown in Table 2, by selecting the specific surfactant alcohol ether glycoside AEG300, the descaling adhesive of the present application can, based on its own wettability and other properties, cause changes in the structure of the mold stain itself and the contact force between the mold stain and the mold during mold cleaning, thereby easily achieving the initial disintegration of the mold surface stain, and the mold stain cleaning rate reaches 100%. However, the selection of other types of surfactants or other types of alcohol ether glycosides will reduce the mold stain cleaning rate.

Claims

1. A scale-removing glue, characterized in that: The components include, by weight: 100 parts of unvulcanized rubber, 40-70 parts of reinforcing filler, 5-30 parts of cleaning agent, 7-20 parts of surfactant, 1-5 parts of vulcanizing agent, and 5-30 parts of auxiliary agent; the surfactant includes alcohol ether glycoside.

2. The scale removal glue according to claim 1, characterized in that The amount of the surfactant is 10-20 parts.

3. The scale removal glue according to claim 2, characterized in that The content of glycoside in the alcohol ether glycoside is 60-75 wt %.

4. The scale removal glue according to claim 1 or 3, characterized in that The weight ratio of the unvulcanized rubber to the reinforcing filler is 1:(0.4-0.6).

5. The scale removal glue according to claim 4, characterized in that The weight ratio of the cleaning agent to the surfactant is (7-13): (10-20).

6. The scale removal glue according to claim 1, characterized in that The unvulcanized rubber includes at least one of butyl rubber, chloroprene rubber, hydrogenated nitrile rubber, natural rubber, fluororubber, silicone rubber, styrene-butadiene rubber, EPDM rubber, and butadiene rubber.

7. The scale removal glue according to claim 1, characterized in that The reinforcing filler includes at least one of white carbon black, nano calcium carbonate, carbon black, diatomaceous earth, talc powder, mica powder and montmorillonite.

8. The scale removal glue according to claim 1, characterized in that The cleaning agent includes at least one of ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, hydroxyethylethylenediamine, methyl isobutyl ketone, ethyl isobutyl ketone, methyl ethyl ketone, acetone, butanone, cyclohexane, propylene oxide, methyl acetate, ethyl acetate, and propyl acetate.

9. A method for preparing the scale-removing glue according to any one of claims 1 to 8, characterized in that: The following steps are involved: The unvulcanized rubber is plasticized; a reinforcing filler, a cleaning agent, a surfactant, an auxiliary agent and a vulcanizing agent are sequentially added to the plasticized unvulcanized rubber, and the descaling rubber is obtained after mixing and molding.

10. An application of the scale removal glue according to any one of claims 1 to 8, characterized in that: Used for mold cleaning operations of semiconductor molds.