Organic silicon stripping liquid as well as preparation method and application thereof

Abstract

The invention relates to an organic silicon stripping liquid as well as a preparation method and application thereof. The organic silicon stripping liquid comprises the following components in percentage by mass: 90-98% of a low-polarity solvent, 1-5% of a surfactant and 1-10% of a penetrant. The low-polarity solvent, the surfactant and the penetrant are compounded according to a specific mass ratio, the penetrant is used for improving the infiltration capacity of the low-polarity solvent, and the penetrant infiltrates into a cross-linked network of organic silicon to generate swelling and then is removed from a substrate; and the surfactant is used for reducing the surface tension of the low-polarity solvent and further promoting the low-polarity solvent to permeate into a cross-linked network of the organic silicon, so that swelling and good demolding effects are generated, and no residue is left on the surface of a base material.

Description

Technical Field

[0001] The present invention belongs to the technical field of stripping fluids, and relates to an organic silicon stripping fluid, a preparation method and an application thereof, and in particular to an environmentally friendly stripping fluid with simple components and capable of quickly and effectively removing organic silicon, and a preparation method and an application thereof. Background Art

[0002] In the chemical industry, silicone is widely used to synthesize silicone polymers, silicone oils, silicone resins and other products, which are widely used in plastics, rubber, coatings, building materials and other fields. In the electronics industry, silicone can be used as packaging and packaging materials, and is widely used in the production process of integrated circuits. Silicone packaging can prevent integrated circuits from being affected by the environment and reduce physical damage caused by various pressures. In addition, in the medical industry, medical silicone materials have excellent biocompatibility, high temperature resistance, chemical corrosion resistance and other characteristics, and are widely used in medical devices, medical consumables and medical auxiliary products.

[0003] As we can see, silicone materials are widely used, but they also have cleaning problems. As for the cleaning problem of silicone, traditional silicone needs to be removed with high-temperature strong acid or strong alkali, which has high safety risks and will cause great damage to other contact materials. At the same time, the components are complex, which will increase the cost of waste liquid treatment.

[0004] CN105349035A discloses a solvent-free silicone stripper and a preparation method thereof. The stripper components include: vinyl-terminated polydimethylsiloxane, vinyl-terminated polymethylvinylsiloxane, sodium methyl silicate, sodium ethyl silicate, methyl hydrogen silicone oil, acrylic acid, sodium chloroplatinate, 1,3-divinyltetramethyldisiloxane, sodium bicarbonate, ethanol, methyl salicylate, pentaerythritol, and diphenylamine. The preparation method is to first mix sodium chloroplatinate, 1,3-divinyltetramethyldisiloxane, sodium bicarbonate and ethanol and heat them to 70-80°C and stir for 10-20 minutes, then add the remaining components after cooling to 25-35°C, and mix and stir evenly to obtain the stripper. The stripper has complex components, high waste liquid treatment costs, and contains unfriendly organic components such as acrylic acid and diphenylamine, which is not environmentally friendly.

[0005] It is very meaningful to develop an environmentally friendly and simple silicone stripping solution. Summary of the invention

[0006] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a silicone stripping solution and a preparation method and application thereof, and in particular to provide an environmentally friendly stripping solution with simple components and capable of quickly and effectively removing silicone and a preparation method and application thereof.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an organic silicon stripping solution, wherein the components of the organic silicon stripping solution include, by mass percentage, 90-98% of a low polarity solvent, 1-5% of a surfactant, and 1-10% of a penetrant.

[0009] The present invention develops a brand-new silicone stripping liquid, which is a compound of 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, penetrate into the cross-linked network of the silicone to produce swelling, and then be removed from the substrate; the surfactant is used to reduce the surface tension of the low-polarity solvent, further promote its penetration into the cross-linked network of the silicone, thereby producing swelling and a good demolding effect, and no residue is left on the surface of the substrate.

[0010] The mass percentage of the low-polarity solvent can be selected from 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% and the like; the mass percentage of the surfactant can be selected from 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and the like; the mass percentage of the penetrant can be selected from 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and the like; other specific point values ​​within the above numerical ranges can be selected, and they will not be described one by one here.

[0011] Preferably, the low polarity solvent includes any one of limonene, benzene, trimethylbenzene, petroleum ether, p-xylene, cyclohexane or n-hexane, or a combination of at least two thereof.

[0012] The low polarity solvent used in the present invention is preferably the above specific type, and more preferably a combination of trimethylbenzene and cyclohexane, which has better swelling and demoulding effects on the organosilicon cross-linked network.

[0013] More preferably, the low polarity solvent is a combination of trimethylbenzene and cyclohexane.

[0014] Preferably, the surfactant includes any one of fatty acid methyl ester ethoxylate, coconut oil diethanolamide, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, isooctyl alcohol polyoxypropylene polyoxyethylene ether or octylphenol polyoxyethylene ether, or a combination of at least two thereof.

[0015] The surfactant used in the present invention is preferably the above-mentioned specific type, and more preferably a combination of coconut oil diethanolamide, sodium dodecylbenzene sulfonate and octylphenol polyoxyethylene ether, which has a better effect in reducing the surface tension of low-polarity solvents and further promoting the penetration of the stripping solution into the silicone cross-linked network.

[0016] More preferably, the surfactant is a combination of coconut oil diethanolamide, sodium dodecylbenzene sulfonate and octylphenol polyoxyethylene ether.

[0017] Preferably, the penetrant comprises sodium di-sec-octyl maleate sulfonate and / or coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate.

[0018] The penetrant used in the present invention is preferably the above-mentioned specific type, and more preferably a combination of sodium di-sec-octyl maleate sulfonate and coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate, which is better in increasing the penetration ability of low-polarity solvents and thus improving the removal effect of silicone and substrate.

[0019] Preferably, the components of the organic silicon stripping solution include, by mass percentage: 92-96% of low polarity solvent, 2-4% of surfactant, and 2-8% of penetrant.

[0020] Preferably, the components of the silicone stripping solution further include, by mass percentage: 0.3-2% of organic additives, such as 0.3%, 0.5%, 1%, 1.2%, 1.5%, 1.7%, 2%, etc.; the organic additives include methimazole and / or iminodiacetic acid.

[0021] Further adding the above-mentioned organic auxiliary agent to the stripping solution of the present invention can further improve the stripping efficiency of silicone.

[0022] In a second aspect, the present invention provides a method for preparing the organic silicon stripping solution according to the first aspect, the preparation method comprising:

[0023] The low-polarity solvent, surfactant, penetrant and optional organic auxiliary agent are stirred and mixed at 10-50°C (e.g., 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 50°C, etc.) for 3-8h (e.g., 3h, 4h, 5h, 6h, 7h, 8h, etc.), and filtered to obtain.

[0024] The preparation method of the organosilicon stripping solution of the present invention is simple and easy to operate, and can realize industrial scale production.

[0025] In a third aspect, the present invention provides use of the organic silicone stripping solution according to the first aspect in stripping an organic silicone film on a surface of a substrate.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The present invention develops a brand-new silicone stripping liquid, which is a compound of 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, penetrate into the cross-linked network of the silicone to produce swelling, and then be removed from the substrate; the surfactant is used to reduce the surface tension of the low-polarity solvent, further promote its penetration into the cross-linked network of the silicone, thereby producing swelling and a good demolding effect, and no residue is left on the surface of the substrate. DETAILED DESCRIPTION

[0028] In order to further explain the technical means and effects adopted by the present invention, the technical solution of the present invention is further described below in conjunction with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

[0029] The coconut oil diethanolamide used in the following examples is a product purchased from Henan Hongjia Chemical Products Co., Ltd. with a model number of 6501; octylphenol polyoxyethylene ether is a product purchased from Hubei Hongjing Chemical Co., Ltd. with a model number of OP-15; sodium di-sec-octyl maleate sulfonate is a product purchased from Jiangsu Hai'an Petrochemical Plant with a model number of OT-75; coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate is a product purchased from Hubei Tuobang Chemical Co., Ltd. with a model number of TB12719.

[0030] Example 1

[0031] The present embodiment provides an organic silicone stripping liquid, whose components, measured by mass percentage, include: 60% of 1,3,5-trimethylbenzene, 34% of cyclohexane, 1% of coconut oil diethanolamide, 1% of sodium dodecylbenzene sulfonate, 1% of octylphenol polyoxyethylene ether, 2% of sodium di-sec-octyl maleate sulfonate, and 1% of coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate.

[0032] The preparation method is as follows:

[0033] Start stirring the reaction kettle and set the speed to 600 rpm; add the above components according to the proportion, stir and mix at 25°C for 5 hours, transfer the above liquid to a special filtration kettle for filtration, and obtain the product.

[0034] Example 2

[0035] The present embodiment provides an organic silicone stripping liquid, whose components, measured by mass percentage, include: 60% benzene, 31% n-hexane, 1% coconut oil diethanolamide, 1% sodium dodecylbenzene sulfonate, 2% octylphenol polyoxyethylene ether, 3% sodium di-sec-octyl maleate sulfonate, and 2% coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate.

[0036] The preparation method is as follows:

[0037] Start stirring the reaction kettle and set the speed to 600 rpm; add the above components according to the proportion, stir and mix at 30°C for 4 hours, transfer the above liquid to a special filtration kettle for filtration, and obtain the product.

[0038] Example 3

[0039] The present embodiment provides an organic silicon stripping liquid, whose components, measured 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-sec-octyl maleate sulfonate, and 2% coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate.

[0040] The preparation method is as follows:

[0041] Start stirring the reaction kettle and set the speed to 600 rpm; add the above components according to the proportion, stir and mix at 20°C for 7 hours, transfer the above liquid to a special filtration kettle for filtration, and obtain the product.

[0042] Example 4

[0043] This embodiment provides an organic silicon stripping liquid, the components of which differ from those of embodiment 1 only in that 60% of 1,3,5-trimethylbenzene and 34% of cyclohexane are replaced with 94% of a single solvent, 1,3,5-trimethylbenzene, and the other components and contents remain unchanged. The preparation method thereof is the same as that of embodiment 1.

[0044] Example 5

[0045] This embodiment provides an organic silicon stripping liquid, the components of which differ from those of embodiment 1 only in that 60% of 1,3,5-trimethylbenzene and 34% of cyclohexane are replaced with 94% of a single solvent, cyclohexane, and the other components and contents remain unchanged. The preparation method thereof is the same as that of embodiment 1.

[0046] Example 6

[0047] This embodiment provides an organic silicon stripping liquid, the components of which differ from those of the embodiment 1 only in that 1% of coconut oil diethanolamide, 1% of sodium dodecylbenzene sulfonate, and 1% of octylphenol polyoxyethylene ether are replaced with 1.5% of coconut oil diethanolamide and 1.5% of sodium dodecylbenzene sulfonate, and the other components and contents remain unchanged. The preparation method thereof is the same as that of the embodiment 1.

[0048] Example 7

[0049] This embodiment provides an organic silicon stripping liquid, the components of which differ from those of the embodiment 1 only in that 1% coconut oil diethanolamide, 1% sodium dodecylbenzene sulfonate, and 1% octylphenol polyoxyethylene ether are replaced with 1.5% coconut oil diethanolamide and 1.5% octylphenol polyoxyethylene ether, and the other components and contents remain unchanged. The preparation method thereof is the same as that of the embodiment 1.

[0050] Example 8

[0051] This embodiment provides an organic silicon stripping liquid, the components of which differ from those of the embodiment 1 only in that 1% of coconut oil diethanolamide, 1% of sodium dodecylbenzene sulfonate, and 1% of octylphenol polyoxyethylene ether are replaced with 1.5% of sodium dodecylbenzene sulfonate and 1.5% of octylphenol polyoxyethylene ether, and the other components and contents remain unchanged. The preparation method thereof is the same as that of the embodiment 1.

[0052] Example 9

[0053] This embodiment provides an organic silicon stripping liquid, the components of which differ from those of the embodiment 1 only in that 2% of di-secondary octyl maleate sulfonate sodium and 1% of coconut oil alkyl dihydroxyethyl methyl chloride quaternary ammonium salt ethoxylate are replaced with 3% of di-secondary octyl maleate sulfonate sodium, and the other components and contents remain unchanged. The preparation method thereof is the same as that of the embodiment 1.

[0054] Example 10

[0055] This embodiment provides an organic silicon stripping liquid, the components of which differ from those of the embodiment 1 only in that 2% of di-sec-octyl maleate sulfonate sodium and 1% of coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate are replaced with 3% of coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate, and the other components and contents remain unchanged. The preparation method thereof is the same as that of the embodiment 1.

[0056] Embodiment 11

[0057] This embodiment provides an organic silicon stripping liquid, the components of which are different from those of the embodiment 1 only in that 1% methimazole is further added, the content of 1,3,5-trimethylbenzene is correspondingly reduced by 1%, and the other components and contents remain unchanged. The preparation method is the same as that of the embodiment 1.

[0058] Example 12

[0059] This embodiment provides an organic silicon stripping liquid, the components of which are different from those of embodiment 1 only in that 1% of iminodiacetic acid is further added, the content of 1,3,5-trimethylbenzene is correspondingly reduced by 1%, and the other components and contents remain unchanged. The preparation method is the same as that of embodiment 1.

[0060] Embodiment 13

[0061] This embodiment provides an organic silicon stripping liquid, the components of which differ from those of embodiment 1 only in that 0.5% iminodiacetic acid and 0.5% methimazole are further added, the content of 1,3,5-trimethylbenzene is reduced by 1% accordingly, and the other components and contents remain unchanged. The preparation method is the same as that of embodiment 1.

[0062] Comparative Example 1

[0063] This comparative example provides an organic silicon stripping liquid, the components of which differ from those of Example 1 only in that a surfactant is missing, the reduced amount of which is supplemented by 1,3,5-trimethylbenzene and cyclohexane in proportion, and the other components and contents remain unchanged. The preparation method is the same as that of Example 1.

[0064] Comparative Example 2

[0065] This comparative example provides an organic silicon stripping liquid, the components of which differ from those of Example 1 only in that a penetrant is missing, the reduced amount of which is supplemented by 1,3,5-trimethylbenzene and cyclohexane in proportion, and the other components and contents remain unchanged. The preparation method is the same as that of Example 1.

[0066] Test Case

[0067] A sapphire substrate (4 inches, Al2O3) coated with a 30 μm thick organic silicone film (made by coating, pre-baking at 70°C and curing at 190°C using temporary bonding material WLP TB5160 provided by Shenzhen Huaxun Semiconductor Materials Co., Ltd.) was immersed in the stripping solution prepared in Examples 1-13 and Comparative Examples 1-2, and the film was observed after being immersed for 5 min and 20 min at 25°C. If the film could be detached, the sapphire substrate was rinsed at the detached position with IPA for 3 min and dried with nitrogen, and then 5 different detached positions were selected for XPS testing to confirm whether there was silicon residue on the surface. The 20-min test results are shown in Table 1, and the 5-min test results are shown in Table 2.

[0068] Table 1

[0069]

[0070]

[0071] It can be seen from the data results in Table 1 that, compared with Comparative Examples 1-2, the stripping liquid involved in Examples 1-13 has a significantly excellent stripping effect on the organic silicone film at room temperature, and the organic silicone film is completely or substantially completely stripped without any silicon element remaining.

[0072] Table 2

[0073]

[0074]

[0075] It can be seen from the data results in Table 2 that compared with the data in Table 1, under a shorter immersion time, the stripping liquids involved in Examples 1-13 also have more obvious and excellent stripping effects on the organic silicone film at room temperature than the stripping liquids of Comparative Examples 1-2; among them, Example 13 has the best stripping effect, the organic silicone film has a better shedding effect, and no silicon element remains; the data comparison results of different embodiments also show that the formula of low-polarity solvents, the formula of surfactants, and the formula of penetrants also affect the stripping efficiency to a certain extent.

[0076] The applicant declares that the present invention illustrates the technical solution of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0077] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0078] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A silicone stripping solution, characterized in that: The components of the organic silicon stripping solution include, by mass percentage, 90-98% of a low-polarity solvent, 1-5% of a surfactant, and 1-10% of a penetrant.

2. The organic silicon stripping solution according to claim 1, characterized in that: The low polarity solvent includes any one of limonene, benzene, trimethylbenzene, petroleum ether, p-xylene, cyclohexane or n-hexane, or a combination of at least two thereof.

3. The organic silicon stripping solution according to claim 2, characterized in that: The low polarity solvent is a combination of trimethylbenzene and cyclohexane.

4. The organic silicon stripping solution according to any one of claims 1 to 3, characterized in that: The surfactant includes any one of fatty acid methyl ester ethoxylate, coconut oil diethanolamide, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, isooctyl alcohol polyoxypropylene polyoxyethylene ether or octylphenol polyoxyethylene ether, or a combination of at least two thereof.

5. The organic silicon stripping solution according to claim 4, characterized in that: The surfactant is a combination of coconut oil diethanolamide, sodium dodecylbenzene sulfonate and octylphenol polyoxyethylene ether.

6. The organic silicon stripping solution according to any one of claims 1 to 5, characterized in that: The penetrant includes sodium di-sec-octyl maleate sulfonate and / or coconut oil alkyl dihydroxyethyl methyl quaternary ammonium chloride ethoxylate.

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

8. The organic silicon stripping solution according to any one of claims 1 to 7, characterized in that: The components of the organic silicon stripping solution further include, by weight percentage: 0.3-2% of an organic auxiliary agent; the organic auxiliary agent includes methimazole and / or iminodiacetic acid.

9. The method for preparing an organic silicon stripping solution according to any one of claims 1 to 8, characterized in that: The preparation method comprises: The low polarity solvent, surfactant, penetrant and optional organic additive are stirred and mixed at 10-50° C. for 3-8 hours, and filtered to obtain the product.

10. Use of the organic silicon stripping solution according to any one of claims 1 to 8 in stripping an organic silicon film on a substrate surface.

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