Silicone release agent, and preparation method therefor and use thereof

Abstract

The present application relates to a silicone release agent, and a preparation method therefor and use thereof. A component of the silicone release agent comprises: a low-polarity solvent 90-98%, a surfactant 1-5%, and a penetrant 1-10%, by mass percentage. In the present application, the low-polarity solvent, the surfactant, and the penetrant are compounded in a specific mass ratio, wherein the penetrant is used to enhance the penetration capability of the low-polarity solvent, enabling it to penetrate the cross-linked network of the silicone, induce swelling, and thereby releasing from the substrate; the surfactant is used to reduce the surface tension of the low-polarity solvent, further promoting its penetration into the cross-linked network of the silicone, which leads to swelling and effective release, while leaving no residue on the substrate surface.

Description

An organosilicon stripping liquid, its preparation method and application Technical Field

[0001] This application belongs to the field of stripping liquid technology, and relates to an organosilicon stripping liquid, its preparation method and application, and in particular to an environmentally friendly, simple-component, fast and effective stripping liquid for removing organosilicon, its preparation method and application. Background Technology

[0002] In the chemical industry, silicone is widely used in the synthesis of silicone polymers, silicone oils, and silicone resins, which are then widely applied in plastics, rubber, coatings, and building materials. In the electronics industry, silicone is used as encapsulation and packaging materials, widely applied in integrated circuit manufacturing. Silicone encapsulation protects integrated circuits from environmental influences and mitigates physical damage caused by various pressures. Furthermore, in the medical industry, medical silicone materials possess excellent biocompatibility, high-temperature resistance, and chemical corrosion resistance, making them widely used in medical devices, medical consumables, and medical auxiliary products.

[0003] As can be seen, silicone materials have a wide range of applications, but they also present cleaning challenges. Traditional silicone cleaning methods require high-temperature, strong acid or alkali treatments, posing significant safety risks and causing substantial damage to other contact materials. Furthermore, the complex composition of silicone increases wastewater treatment costs.

[0004] CN105349035A discloses a solvent-free silicone stripping agent and its preparation method. The stripping agent components include: vinyl-terminated polydimethylsiloxane, vinyl-terminated polymethylvinylsiloxane, sodium methylsilicate, sodium ethylsilicate, methyl hydrogen silicone oil, acrylic acid, sodium chloroplatinate, 1,3-divinyltetramethyldisiloxane, sodium bicarbonate, ethanol, methyl salicylate, pentaerythritol, and diphenylamine. The preparation method involves first mixing sodium chloroplatinate, 1,3-divinyltetramethyldisiloxane, sodium bicarbonate, and ethanol, heating to 70-80℃, stirring for 10-20 minutes, and then cooling to 25-35℃ before adding the remaining components and mixing thoroughly. This stripping agent has a complex composition, high wastewater treatment costs, and contains unfriendly organic components such as acrylic acid and diphenylamine, making it less environmentally friendly.

[0005] Therefore, it would be very meaningful to develop an environmentally friendly and simple silicone stripping solution. Summary of the Invention

[0006] This application provides an organosilicon stripping liquid, its preparation method, and its application, and in particular, provides an environmentally friendly, simple-component, and fast-acting organosilicon stripping liquid, its preparation method, and its application.

[0007] In a first aspect, this application provides an organosilicon stripping liquid, the components of which, by mass percentage, comprise: 90-98% low-polarity solvent, 1-5% surfactant, and 1-10% penetrant.

[0008] This application develops a novel silicone stripping liquid, which combines a low-polarity solvent, a surfactant, and a penetrant in a specific mass ratio. The penetrant is used to increase the penetration ability of the low-polarity solvent, allowing it to penetrate into the cross-linked network of the silicone and swell, thereby removing it from the substrate. The surfactant is used to reduce the surface tension of the low-polarity solvent, further promoting its penetration into the cross-linked network of the silicone, thereby producing swelling and a good demolding effect, with no residue on the substrate surface.

[0009] The mass percentage of the low-polarity solvent can be selected from 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, or 98%, etc.; the mass percentage of the surfactant can be selected from 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%, etc.; the mass percentage of the penetrant can be selected from 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, etc.; other specific values ​​within the above ranges can also be selected, and will not be elaborated here.

[0010] Preferably, the low-polarity solvent includes any one or a combination of at least two of limonene, benzene, thylene, petroleum ether, p-xylene, cyclohexane, or n-hexane.

[0011] The low-polarity solvents used in this application are preferably of the specific types mentioned above, and more preferably a combination of tricresylbenzene and cyclohexane, which has a better effect on swelling and demolding of organosilicon crosslinked networks.

[0012] More preferably, the low-polarity solvent is a combination of tricresylbenzene and cyclohexane.

[0013] Preferably, the surfactant comprises any one or a combination of at least two of fatty acid methyl ester ethoxylate, coconut oil diethanolamide, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, isooctanol polyoxypropylene polyoxyethylene ether, or octylphenol polyoxyethylene ether.

[0014] The surfactants used in this application are preferably of the specific types mentioned above, and more preferably a combination of coconut oil diethanolamide, sodium dodecylbenzene sulfonate and octylphenol polyoxyethylene ether, which has a better effect on reducing the surface tension of low polar solvents and further promoting the penetration of the stripping liquid into the organosilicon crosslinking network.

[0015] More preferably, the surfactant is a combination of coconut oil diethanolamide, sodium dodecylbenzenesulfonate, and octylphenol polyoxyethylene ether.

[0016] Preferably, the penetrant comprises sodium dioctyl maleate sulfonate and / or coconut oil alkyl dihydroxyethyl methyl chloride ethoxylate.

[0017] The penetrant used in this application is preferably of the specific type mentioned above, and more preferably a combination of sodium dioctyl maleate sulfonate and cocoyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate, which is superior in increasing the penetrating power of low polar solvents and thus improving the removal effect of organosilicon from the substrate.

[0018] Preferably, the components of the silicone stripping solution, by mass percentage, include: 92-96% low-polarity solvent, 2-4% surfactant, and 2-8% penetrant.

[0019] Preferably, the components of the silicone stripping solution further include, by mass percentage: 0.3-2% organic additives, such as 0.3%, 0.5%, 1%, 1.2%, 1.5%, 1.7%, or 2%; the organic additives include methimazole and / or iminodiacetic acid.

[0020] Adding the aforementioned organic additives to the stripping solution described in this application can further improve the stripping efficiency of organosilicon.

[0021] Secondly, this application provides a method for preparing the organosilicon stripping liquid according to the first aspect, the preparation method comprising:

[0022] The low-polarity solvent, surfactant, penetrant, and optional organic additives are stirred and mixed at 10-50°C (e.g., 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, or 50°C) for 3-8 hours (e.g., 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours), and then filtered to obtain the final product.

[0023] The preparation method of the organosilicon stripping liquid involved in this application is simple and easy to operate, and can be industrialized and scaled up for production.

[0024] Thirdly, this application provides the use of the silicone stripping liquid according to the first aspect in the stripping of silicone film on the surface of a substrate.

[0025] Compared with the prior art, this application has the following beneficial effects:

[0026] This application develops a novel silicone stripping liquid, which combines a low-polarity solvent, a surfactant, and a penetrant in a specific mass ratio. The penetrant is used to increase the penetration ability of the low-polarity solvent, allowing it to penetrate into the cross-linked network of the silicone and swell, thereby removing it from the substrate. The surfactant is used to reduce the surface tension of the low-polarity solvent, further promoting its penetration into the cross-linked network of the silicone, thereby producing swelling and a good demolding effect, with no residue on the substrate surface. Detailed Implementation

[0027] To further illustrate the technical means and effects adopted in this application, the following describes the technical solution of this application in conjunction with preferred embodiments, but this application is not limited to the scope of the embodiments.

[0028] The coconut oil diethanolamide used in the following examples was product 6501 purchased from Henan Hongjia Chemical Products Co., Ltd.; octylphenol polyoxyethylene ether was product OP-15 purchased from Hubei Hongjing Chemical Co., Ltd.; sodium di-2-octyl maleate sulfonate was product OT-75 purchased from Jiangsu Haian Petrochemical Plant; and coconut oil alkyl dihydroxyethyl methyl chloride quaternary ammonium salt ethoxylate was product TB12719 purchased from Hubei Tuobang Chemical Co., Ltd.

[0029] Example 1

[0030] This embodiment provides an organosilicon stripping solution, the components of which, by mass percentage, include: 60% 1,3,5-trimethylbenzene, 34% cyclohexane, 1% coconut oil diethanolamide, 1% sodium dodecylbenzene sulfonate, 1% octylphenol polyoxyethylene ether, 2% sodium di-2-octyl maleate sulfonate, and 1% coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate.

[0031] Its preparation method is as follows:

[0032] Start the reactor stirring and set the speed to 600 rpm; add the above components according to the ratio, stir and mix at 25°C for 5 hours, and transfer the above liquid to a special filtration vessel for filtration to obtain the final product.

[0033] Example 2

[0034] This embodiment provides an organosilicon stripping liquid, the components of which, by mass percentage, include: 60% benzene, 31% hexane, 1% coconut oil diethanolamide, 1% sodium dodecylbenzene sulfonate, 2% octylphenol polyoxyethylene ether, 3% sodium dioctyl maleate sulfonate, or 2% coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate.

[0035] Its preparation method is as follows:

[0036] Start the reactor stirring and set the speed to 600 rpm; add the above components according to the ratio, stir and mix at 30°C for 4 hours, and transfer the above liquid to a special filtration vessel for filtration to obtain the final product.

[0037] Example 3

[0038] This embodiment provides an organosilicon stripping solution, the components of which, by mass percentage, include: 60% p-xylene, 32% petroleum ether, 1% coconut oil diethanolamide, 1% sodium dodecylbenzene sulfonate, 2% octylphenol polyoxyethylene ether, 2% sodium di-2-octyl maleate sulfonate, or 2% coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate.

[0039] Its preparation method is as follows:

[0040] Start the reactor stirring and set the speed to 600 rpm; add the above components according to the ratio, stir and mix at 20°C for 7 hours, and transfer the above liquid to a special filtration vessel for filtration to obtain the final product.

[0041] Example 4

[0042] This embodiment provides an organosilicon stripping solution, the only difference from Example 1 being the replacement of 60% 1,3,5-trimethylbenzene and 34% cyclohexane with a single solvent, 94% 1,3,5-trimethylbenzene; all other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0043] Example 5

[0044] This embodiment provides an organosilicon stripping solution, the only difference from Example 1 being the replacement of 60% 1,3,5-trimethylbenzene and 34% cyclohexane with a single solvent, 94% cyclohexane, while the other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0045] Example 6

[0046] This embodiment provides an organosilicon stripping solution, the only difference from Example 1 being that 1% coconut oil diethanolamide, 1% sodium dodecylbenzenesulfonate, and 1% octylphenol polyoxyethylene ether are replaced with 1.5% coconut oil diethanolamide and 1.5% sodium dodecylbenzenesulfonate, while other components and contents remain unchanged. The preparation method is the same as in Example 1.

[0047] Example 7

[0048] This embodiment provides an organosilicon stripping solution, the only difference from Example 1 being that 1% coconut oil diethanolamide, 1% sodium dodecylbenzenesulfonate, and 1% octylphenol polyoxyethylene ether are replaced with 1.5% coconut oil diethanolamide and 1.5% octylphenol polyoxyethylene ether, while other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0049] Example 8

[0050] This embodiment provides an organosilicon stripping solution, the only difference from Example 1 being that 1% coconut oil diethanolamide, 1% sodium dodecylbenzenesulfonate, and 1% octylphenol polyoxyethylene ether are replaced with 1.5% sodium dodecylbenzenesulfonate and 1.5% octylphenol polyoxyethylene ether, while other components and contents remain unchanged. The preparation method is the same as in Example 1.

[0051] Example 9

[0052] This embodiment provides an organosilicon stripping solution, the only difference from Example 1 being that 2% sodium di-2-octyl maleate sulfonate and 1% cocoyl dihydroxyethyl methyl chloride quaternary ammonium salt ethoxylate are replaced with a single penetrant, 3% sodium di-2-octyl maleate sulfonate; all other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0053] Example 10

[0054] This embodiment provides an organosilicon stripping solution, the only difference from Example 1 being that 2% sodium di-2-octyl maleate sulfonate and 1% cocoyl dihydroxyethyl methyl chloride ethoxylate are replaced with a single penetrant, 3% cocoyl dihydroxyethyl methyl chloride ethoxylate. All other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0055] Example 11

[0056] This embodiment provides an organosilicon stripping solution, the only difference from that of Example 1 being the addition of 1% methimazole, with the content of 1,3,5-trimethylbenzene reduced by 1% accordingly, while the other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0057] Example 12

[0058] This embodiment provides an organosilicon stripping solution, the only difference from Example 1 being the addition of 1% iminodiacetic acid, with the content of 1,3,5-trimethylbenzene reduced by 1% accordingly, while other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0059] Example 13

[0060] This embodiment provides an organosilicon stripping solution, the only difference from Example 1 being the addition of 0.5% iminodiacetic acid and 0.5% methimazole, with the content of 1,3,5-trimethylbenzene reduced by 1% accordingly, while other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0061] Comparative Example 1

[0062] This comparative example provides an organosilicon stripping solution, the only difference from Example 1 being the absence of a surfactant. The reduced amount is made up by 1,3,5-trimethylbenzene and cyclohexane in proportion, while the other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0063] Comparative Example 2

[0064] This comparative example provides an organosilicon stripping solution, the only difference from Example 1 being the absence of a penetrant. The reduced amount is made up by 1,3,5-trimethylbenzene and cyclohexane in proportion, while the other components and their contents remain unchanged. The preparation method is the same as in Example 1.

[0065] Test case

[0066] A sapphire substrate (4-inch, Al2O3) coated with a 30μm thick silicone film (prepared by coating, pre-baking at 70℃ and curing at 190℃ using temporary bonding material WLP TB5160 provided by Shenzhen Huaxun Semiconductor Materials Co., Ltd.) was immersed in the stripping solutions prepared in Examples 1-13 and Comparative Examples 1-2. After immersion at 25℃ for 5 min and 20 min respectively, the film detachment was observed. If detachment was possible, the detached area of ​​the sapphire substrate was rinsed with IPA for 3 min and dried with nitrogen. Then, XPS tests were performed on 5 different detachment locations to confirm whether there was any silicon residue on the surface. The test results for 20 min are shown in Table 1, and the test results for 5 min are shown in Table 2.

[0067] Table 1

[0068] As shown in Table 1, compared with Comparative Examples 1-2, the stripping solutions involved in Examples 1-13 have significantly better stripping effects on silicone films at room temperature. The silicone films are completely or almost completely removed without any silicon residue.

[0069] Table 2

[0070] As shown in Table 2, compared with the data in Table 1, the stripping solutions involved in Examples 1-13 exhibit superior stripping effects on silicone films at room temperature compared to the stripping solutions in Comparative Examples 1-2, even with shorter soaking times. Among them, Example 13 showed the best stripping effect, with better removal of the silicone film and no silicon residue. The data comparison results of different examples also indicate that the formulation of low-polarity solvents, surfactants, and penetrants also affect the stripping efficiency to a certain extent.

[0071] The applicant declares that this application illustrates the technical solution of this application through the above embodiments, but this application is not limited to the above embodiments, that is, it does not mean that this application must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to this application, equivalent substitutions of the raw materials of this application's products, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of this application.

[0072] The preferred embodiments of this application have been described in detail above. However, this application is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, and these simple modifications all fall within the protection scope of this application.

[0073] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this application will not describe the various possible combinations separately.

Claims

1. An organosilicon stripping liquid, the components of which, by mass percentage, comprise: 90-98% low-polarity solvent, 1-5% surfactant, and 1-10% penetrant.

2. The silicone stripping solution according to claim 1, wherein, The low-polarity solvent includes any one or a combination of at least two of limonene, benzene, thylene, petroleum ether, p-xylene, cyclohexane, or n-hexane.

3. The silicone stripping solution according to claim 2, wherein, The low-polarity solvent is a combination of tricresyl and cyclohexane.

4. The silicone stripping solution according to any one of claims 1-3, wherein, The surfactant includes any one or a combination of at least two of the following: fatty acid methyl ester ethoxylate, coconut oil diethanolamide, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, isooctanol polyoxypropylene polyoxyethylene ether, or octylphenol polyoxyethylene ether.

5. The silicone stripping solution according to claim 4, wherein, The surfactant is a combination of coconut oil diethanolamide, sodium dodecylbenzenesulfonate, and octylphenol polyoxyethylene ether.

6. The silicone stripping solution according to any one of claims 1-5, wherein, The penetrant includes sodium dioctyl maleate sulfonate and / or cocoyl dihydroxyethyl methyl chloride ethoxylate.

7. The silicone stripping solution according to any one of claims 1-6, wherein, The components of the silicone stripping solution, by mass percentage, include: 92-96% low-polarity solvent, 2-4% surfactant, and 2-8% penetrant.

8. The silicone stripping solution according to any one of claims 1-7, wherein, The components of the silicone stripping solution, by mass percentage, further include: 0.3-2% organic additives; the organic additives include methimazole and / or iminodiacetic acid.

9. A method for preparing the silicone stripping solution according to any one of claims 1-8, comprising: The low-polarity solvent, surfactant, penetrant, and optional organic additives are stirred and mixed at 10-50℃ for 3-8 hours, then filtered to obtain the final product.

10. The application of the silicone stripping liquid according to any one of claims 1-8 in the stripping of silicone film on substrate surface.