Silica gel dissolving agent and its preparation method and application

Abstract

The present invention relates to a silica gel dissolving agent and a preparation method and application thereof. The silica gel dissolving agent comprises, by mass percentage, 10% to 40% of organic acid, 47% to 80% of organic solvent, 0.2% to 3% of corrosion inhibitor and 1% to 10% of stabilizer; the boiling point of the organic solvent under standard atmospheric pressure is greater than 100°C. Through the reasonable proportion of the components, the silica gel dissolving agent has a high boiling point, is not easy to volatilize, has a low VOC, and has good temperature resistance; and the silica gel dissolving agent has a fast dissolving speed for silica gel, and is suitable for dissolving silica gel on semiconductor devices.

Description

Technical Field

[0001] The invention relates to the technical field, and in particular to a silica gel dissolving agent and a preparation method and application thereof. Background Art

[0002] Organic silicon gel materials have become indispensable packaging insulation materials in semiconductor devices due to their excellent heat resistance, waterproof and electrical insulation properties. Undesirable phenomena will inevitably occur during the device packaging process, which requires the solidified silicone on the defective device to be dissolved. The solidified silicone has a strong network space structure and is difficult to dissolve using conventional solvents. The special silicone dissolving agent commonly used on the market is usually composed of a mixture of benzenesulfonic acid and low molecular weight halogenated hydrocarbons. This special silicone dissolving agent has the problems of poor temperature resistance and is not environmentally friendly. Summary of the invention

[0003] Based on this, it is necessary to provide a silica gel dissolving agent with good temperature resistance and good silica gel dissolving effect, as well as a preparation method and application thereof.

[0004] In one aspect of the present invention, a silica gel dissolving agent is provided, which comprises the following components in terms of mass percentage:

[0005]

[0006] Wherein, the boiling point of the organic solvent under standard atmospheric pressure is greater than 100°C.

[0007] In any embodiment, the organic acid includes at least one of citric acid, aminosulfonic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, tartaric acid, acetic acid, succinic acid and 1,3-propane sultone.

[0008] In any embodiment, the organic solvent includes at least one of propylene carbonate, dimethyl glutarate, dimethyl succinate, dimethyl adipate, ethylene carbonate, diethylene glycol, 1,4-butanediol, 1,2-propylene glycol, glycerol, 1,4-dioxane, phenylhydrazine and cyclopentane sulfone.

[0009] In any embodiment, the corrosion inhibitor includes at least one of ethylenediaminetetraacetic acid, hexamethylenetetramine, thiadiazole, benzotriazole, 2-mercaptobenzothiazole, tetramethylthiourea, methylbenzotriazole and 2-mercaptobenzimidazole.

[0010] In any embodiment, the stabilizer includes at least one of diethyl phosphate, tributyl phosphate, 2,2,2-trichloroethanol, hydroxyethylidene diphosphonic acid, propylene glycol diacetate, ethylene glycol vinyl ether, propylene glycol methyl ether acetate and ethylene glycol ethyl ether.

[0011] In any embodiment, the silica gel dissolving agent satisfies at least one of the conditions (1) to (4):

[0012] (1) The mass content of the organic acid is 30% to 40%;

[0013] (2) The mass content of the organic solvent is 45% to 65%;

[0014] (3) The mass content of the corrosion inhibitor is 1.5% to 3%;

[0015] (4) The mass content of the stabilizer is 5% to 10%.

[0016] In any embodiment, the boiling point of the silica gel dissolving agent at standard atmospheric pressure is greater than 100°C.

[0017] In any embodiment, the pH value of the silica gel dissolving agent at 25° C. is 0.1-4.

[0018] In a second aspect, the present invention further provides a method for preparing the silica gel dissolving agent of the first aspect, comprising the following steps:

[0019] The organic acid, the organic solvent, the corrosion inhibitor and the stabilizer are mixed to prepare the silica gel dissolving agent.

[0020] In a third aspect, the present invention further provides use of the silica gel dissolving agent of the first aspect in the preparation of semiconductor devices.

[0021] The silica gel dissolving agent comprises organic acid, organic solvent, corrosion inhibitor and stabilizer in a specific ratio, and the boiling point of the organic solvent under standard atmospheric pressure is greater than 100°C. Through the reasonable ratio of the components, the silica gel dissolving agent has a high boiling point, is not easy to volatilize, has a low VOC, and has good temperature resistance; and the silica gel dissolving agent has a fast dissolving speed for silica gel, and is suitable for dissolving silica gel on semiconductor devices. DETAILED DESCRIPTION

[0022] For ease of understanding of the present invention, the present invention will be described more fully below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0024] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features. Unless otherwise specified, the "include" and "comprise" mentioned in the present invention represent open or closed. For example, the "include" and "comprises" may mean that other components not listed may also be included or comprised, or may only include or comprise the listed components.

[0025] In the present invention, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0026] The percentage content involved in the present invention, unless otherwise specified, refers to mass percentage for solid-liquid mixing and solid-solid mixing, and refers to volume percentage for liquid-liquid mixing.

[0027] The percentage concentrations involved in the present invention, unless otherwise specified, refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

[0028] The temperature parameters in the present invention, if not specifically limited, allow for both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows the temperature to fluctuate within the precision range controlled by the instrument.

[0029] An embodiment of the present invention provides a silica gel dissolving agent, which comprises the following components in terms of mass percentage:

[0030]

[0031] The boiling point of the organic solvent at standard atmospheric pressure (101.325 kPa) is greater than 100°C.

[0032] In some embodiments, the boiling point of the organic solvent at standard atmospheric pressure is 101° C. to 300° C. Optionally, the boiling point of the organic solvent at standard atmospheric pressure is within the range of any of the following numerical values: 101° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C., 200° C., 210° C., 240° C., 250° C., 270° C., 280° C. or 300° C.

[0033] The silica gel dissolving agent comprises organic acid, organic solvent, corrosion inhibitor and stabilizer in a specific ratio, and the boiling point of the organic solvent under standard atmospheric pressure is greater than 100°C. Through the reasonable ratio of the components, the silica gel dissolving agent has a high boiling point, is not easy to volatilize, has a low VOC, and has good temperature resistance; and the silica gel dissolving agent has a fast dissolving speed for silica gel, and is suitable for dissolving silica gel on semiconductor devices.

[0034] Organic acid can promote the fracture of the spatial network structure of silica gel. In an embodiment of the present invention, the mass content of organic acid in the silica gel dissolving agent is 10% to 40%. The content of organic acid is within the above range, and it can effectively promote the dissolution of silica gel in combination with other components of the silica gel dissolving agent. If the organic acid content is too low, it is difficult to break the Si-O bond in silica gel; if the organic acid content is too high, the silica gel dissolving agent is more corrosive. Optionally, the mass content of organic acid in the silica gel dissolving agent is within the range of any of the following numerical values: 10%, 12%, 15%, 16%, 18%, 20%, 24%, 25%, 27%, 28%, 30%, 32%, 35%, 36% or 40%. Further, the mass content of organic acid in the silica gel dissolving agent is 30% to 40%.

[0035] In some embodiments, the organic acid includes at least one of citric acid, aminosulfonic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, tartaric acid, acetic acid, succinic acid and 1,3-propane sultone. Further, the organic acid includes dodecylbenzenesulfonic acid. Dodecylbenzenesulfonic acid can not only promote the breakage of the spatial network structure of silica gel, but its alkyl chain also helps the silica gel dissolving agent to penetrate into the silica gel, and the dissolving effect is better.

[0036] The organic solvent can quickly penetrate into the spatial network structure of silica gel to swell the silica gel. In an embodiment of the present invention, the mass content of the organic solvent in the silica gel dissolving agent is 47% to 80%. The content of the organic solvent is within the above range, and it can effectively promote the dissolution of silica gel in combination with other components of the silica gel dissolving agent. If the content of the organic solvent is too low, it cannot completely penetrate into the spatial structure of the silica gel to swell it; if the content of the organic solvent is too high, the content of the corresponding other components is reduced, and the dissolution effect of the silica gel dissolving agent is not ideal. Optionally, the mass content of the organic solvent in the silica gel dissolving agent is within the range of any of the following numerical values: 47%, 48%, 50%, 52%, 54%, 55%, 56%, 60%, 64%, 65%, 70%, 72%, 75%, 77% or 80%. Further, the mass content of the organic solvent in the silica gel dissolving agent is 47% to 65%.

[0037] In some embodiments, the organic solvent includes at least one of propylene carbonate, dimethyl glutarate, dimethyl succinate, dimethyl adipate, ethylene carbonate, diethylene glycol, 1,4-butanediol, 1,2-propylene glycol, glycerol, 1,4-dioxane, phenylhydrazine and sulfolane. The above organic solvent not only has a higher boiling point and better permeability, but also has good compatibility with other components of the silica gel dissolving agent, and can effectively dissolve other components in the silica gel dissolving agent.

[0038] Since the silica gel dissolving agent contains acidic organic acid components, the corrosion inhibitor can prevent metal corrosion in the device treated with the silica gel dissolving agent. In an embodiment of the present invention, the mass content of the corrosion inhibitor in the silica gel dissolving agent is 0.2% to 3%. The content of the corrosion inhibitor within the above range can effectively prevent the silica gel dissolving agent from corroding the metal of the device. Optionally, the mass content of the corrosion inhibitor in the silica gel dissolving agent is within the range of any of the following numerical values: 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 1.6%, 1.8%, 2%, 2.4%, 2.5%, 2.7%, 2.8% or 3%. Further, the mass content of the corrosion inhibitor in the silica gel dissolving agent is 1.5% to 3%.

[0039] In some embodiments, the corrosion inhibitor includes at least one of ethylenediaminetetraacetic acid, hexamethylenetetramine, thiadiazole, benzotriazole, 2-mercaptobenzothiazole, tetramethylthiourea, methylbenzotriazole and 2-mercaptobenzimidazole. Further, the corrosion inhibitor includes tetramethylthiourea.

[0040] The stabilizer can promote the mutual dissolution of the components in the silica gel dissolving agent and maintain the stability of the silica gel dissolving agent. In an embodiment of the present invention, the mass content of the stabilizer in the silica gel dissolving agent is 1% to 10%. When the stabilizer content is within the above range, the stability of the silica gel dissolving agent is better, and the components work synergistically to better dissolve silica gel. If the content of the stabilizer is too low, the silica gel dissolving agent is easy to stratify; if the content of the stabilizer is too high, the content of other components in the silica gel dissolving agent is correspondingly reduced, and the dissolving effect of the silica gel dissolving agent on silica gel is not ideal. Optionally, the mass content of the stabilizer in the silica gel dissolving agent is within the range of any of the following numerical values: 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.8% or 10%. Further, the mass content of the stabilizer in the silica gel dissolving agent is 5% to 10%.

[0041] In some embodiments, the stabilizer includes at least one of diethyl phosphate, tributyl phosphate, 2,2,2-trichloroethanol, hydroxyethylidene diphosphonic acid, propylene glycol diacetate, ethylene glycol vinyl ether, propylene glycol methyl ether acetate and ethylene glycol ethyl ether.

[0042] In some of the embodiments, the silica gel dissolving agent includes, by mass percentage, 30% to 40% dodecylbenzenesulfonic acid, 47% to 60% sulfolane, 0.2% to 3% tetramethylthiourea and 1% to 10% propylene glycol methyl ether acetate.

[0043] In some embodiments, the silica gel dissolving agent includes, by mass percentage, 10% benzenesulfonic acid, 80% sulfolane, 0.2% tetramethylthiourea and 9.8% propylene glycol methyl ether acetate.

[0044] In some embodiments, the boiling point of the silica gel solvent at standard atmospheric pressure (101.325 kPa) is greater than 100°C. The boiling point of the silica gel solvent is greater than 100°C, so the silica gel solvent has a higher boiling point, is not easy to volatilize, has a lower VOC, and is more environmentally friendly. Further, the boiling point of the silica gel solvent at standard atmospheric pressure (101.325 kPa) is 106°C to 293°C.

[0045] In some embodiments, the pH value of the silica gel dissolving agent at 25° C. is 0.1-4.

[0046] One embodiment of the present invention also provides a method for preparing the above-mentioned silica gel dissolving agent, comprising the following steps:

[0047] An organic acid, an organic solvent, a corrosion inhibitor and a stabilizer are mixed to prepare a silica gel dissolving agent.

[0048] In some embodiments, the step of mixing the organic acid, the organic solvent, the corrosion inhibitor and the stabilizer comprises:

[0049] (1) Add the organic acid into a mixing container.

[0050] (2) Add organic solvent, corrosion inhibitor and stabilizer to the mixing container in sequence and stir until they are completely dissolved.

[0051] One embodiment of the present invention further provides use of the above-mentioned silica gel dissolving agent in preparing semiconductor devices.

[0052] The silica gel dissolving agent of the present invention is further described below through specific examples.

[0053] Example

[0054] Preparation of silica gel dissolving agent:

[0055] The silica gel dissolving agents of Examples 1 to 36 and Comparative Examples 1 to 9 are formulated according to Table 1. At room temperature and pressure, an organic acid is added to a mixing tank, and an organic solvent, a corrosion inhibitor and a stabilizer are added in sequence under stirring; the mixture is stirred until completely dissolved and uniformly dissolved, and the mixture is allowed to cool and discharged to obtain a silica gel dissolving agent.

[0056] Test part:

[0057] The boiling points of the silica gel dissolving agents of Examples 1 to 36 and Comparative Examples 1 to 9 at standard atmospheric pressure (101.325 kPa) and pH values ​​at 25° C. were tested respectively.

[0058] Silica gel dissolution test:

[0059] At 25°C, different silica gels of 5mm×5mm×5mm cubes and copper wires with a diameter of 1mm were immersed in the silica gel dissolving agents of Examples 1 to 36 and Comparative Examples 1 to 9 respectively until the silica gel was completely dissolved. The dissolution time and corrosion condition of the copper wire were recorded.

[0060] The compositions of the silica gel dissolving agents of Examples 1 to 36 and Comparative Examples 1 to 9 are recorded in Table 1. The pH values, boiling points and dissolution conditions of the silica gel dissolving agents of Examples 1 to 36 and Comparative Examples 1 to 9 for different silica gels are recorded in Table 2.

[0061] Table 1

[0062]

[0063]

[0064]

[0065]

[0066] Table 2

[0067]

[0068]

[0069]

[0070]

[0071] *The data in the table are the time required for the silicone to completely dissolve, and the corrosion of the copper wire immersed in the silicone solvent during this time.

[0072] It can be seen from the relevant data in Table 1 and Table 2 that the pH value of the silica gel dissolving agents of Examples 1 to 36 at 25°C is 0.11 to 4.0; the boiling point at standard atmospheric pressure is 106°C to 293°C, which has a relatively high boiling point. The silica gel dissolving agents of Examples 1 to 36 can completely dissolve various silica gels by soaking various silica gels for 37min to 77min at 25°C, and have no corrosion to copper wires. It can be seen that the silica gel dissolving agents of Examples 1 to 36 also have a good effect of dissolving silica gel.

[0073] The silica gel dissolving agent of comparative example 1 does not contain a corrosion inhibitor, and has a pH value of 0.53 at 25° C. and a boiling point of 287.2° C. at standard atmospheric pressure. The silica gel dissolving agent of comparative example 1 soaks and dissolves the silica gel for 42 to 78 minutes, but since the pH value of the silica gel dissolving agent is relatively low and does not contain a corrosion inhibitor, the copper wire will be corroded during the dissolving process of the silica gel.

[0074] The silica gel dissolving agent of comparative example 2 does not contain a stabilizer, and has a pH value of 0.53 at 25° C. and a boiling point of 287.2° C. at standard atmospheric pressure. The silica gel dissolving agent of comparative example 2 takes a relatively long time to dissolve silica gel, which is 168 min to 198 min, and does not corrode the copper wire during the dissolution process.

[0075] The component contents of the silica gel dissolving agents of Comparative Examples 3 to 6 are not within the range of the silica gel dissolving agent of the present invention, and the pH value at 25° C. is 0.13 to 0.62; the boiling point at standard atmospheric pressure is 286.1° C. to 297.2° C. The silica gel dissolving agents of Comparative Examples 3 to 6 soak and dissolve the silica gel for 89 min to 699 min, and do not corrode the copper wire during the dissolution process.

[0076] The organic solvent in the silica gel dissolving agent of comparative example 7 is ethanol with a boiling point lower than 100° C. The pH value of the silica gel dissolving agent of comparative example 7 at 25° C. is 0.54; and the boiling point at standard atmospheric pressure is 79° C. The silica gel dissolving agent soaks and dissolves the silica gel for a long time of more than 24 hours, and does not corrode the copper wire during the dissolution process.

[0077] The organic solvent in the silica gel dissolving agent of Comparative Examples 8 to 9 adopts the dichloromethane solvent of the conventional silica gel dissolving agent, and the pH value of the silica gel dissolving agent of Comparative Examples 8 to 9 is 0.1 to 0.46 at 25°C; the boiling point at standard atmospheric pressure is 45°C to 48°C. The silica gel dissolving agent of Comparative Example 8 soaks and dissolves the silica gel for a long time of more than 24 hours, and the copper wire will be corroded during the dissolution process. The silica gel dissolving agent of Comparative Example 9 soaks and dissolves the silica gel for 30min to 40min, and the copper wire will be corroded during the dissolution process.

[0078] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0079] The above-described embodiments only express several implementation methods of the present invention, which are convenient for understanding the technical solutions of the present invention in detail, but they cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are all within the protection scope of the attached claims described in the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the contents of the attached claims, and the description can be used to interpret the contents of the claims.

Claims

1. A silica gel dissolving agent, characterized in that: According to mass percentage, it includes the following components: Organic acid 10%~40%, Organic solvent 47%~80%, Corrosion inhibitor 0.2%~3%, and Stabilizer 1%~10%; Wherein, the boiling point of the organic solvent at standard atmospheric pressure is greater than 100°C; The organic solvent comprises at least one of propylene carbonate, dimethyl glutarate, dimethyl succinate, dimethyl adipate, ethylene carbonate, diethylene glycol, 1,4-butanediol, 1,2-propylene glycol, glycerol, 1,4-dioxane, phenylhydrazine and sulfolane; The organic acid comprises at least one of citric acid, aminosulfonic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, tartaric acid, acetic acid, succinic acid and 1,3-propane sultone; The corrosion inhibitor comprises at least one of ethylenediaminetetraacetic acid, hexamethylenetetramine, thiadiazole, benzotriazole, 2-mercaptobenzothiazole, tetramethylthiourea, methylbenzotriazole and 2-mercaptobenzimidazole; The stabilizer includes at least one of diethyl phosphate, tributyl phosphate, 2,2,2-trichloroethanol, hydroxyethylidene diphosphonic acid, propylene glycol diacetate, ethylene glycol vinyl ether, propylene glycol methyl ether acetate and ethylene glycol ethyl ether.

2. The silica gel dissolving agent according to claim 1, characterized in that The sum of the mass contents of the components of the silica gel dissolving agent is 100%, and the silica gel dissolving agent satisfies at least one of the conditions (1) to (4): (1) The mass content of the organic acid is 30% to 40%; (2) The mass content of the organic solvent is 47% to 65%; (3) The mass content of the corrosion inhibitor is 1.5% to 3%; (4) The mass content of the stabilizer is 5% to 10%.

3. The silica gel dissolving agent according to any one of claims 1 or 2, characterized in that The boiling point of the silica gel dissolving agent under standard atmospheric pressure is greater than 100°C.

4. The silica gel dissolving agent according to any one of claims 1 or 2, characterized in that The pH value of the silica gel dissolving agent at 25° C. is 0.1-4.

5. The silica gel dissolving agent according to claim 1, characterized in that: The silica gel dissolving agent includes, by mass percentage, 30% to 40% dodecylbenzenesulfonic acid, 47% to 60% sulfolane, 0.2% to 3% tetramethylthiourea and 1% to 10% propylene glycol methyl ether acetate.

6. The method for preparing the silica gel dissolving agent according to any one of claims 1 to 5, characterized in that: The following steps are involved: The organic acid, the organic solvent, the corrosion inhibitor and the stabilizer are mixed to prepare the silica gel dissolving agent.

7. Use of the silica gel dissolving agent according to any one of claims 1 to 5 in the preparation of semiconductor devices.

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