Electronic-grade glass fiber cloth surface treating agent for automobile sheet and preparation method of electronic-grade glass fiber cloth surface treating agent

Abstract

The invention discloses an electronic-grade glass fiber cloth surface treating agent for an automobile sheet and a preparation method of the electronic-grade glass fiber cloth surface treating agent. The surface treating agent comprises a first impregnation tank treating fluid and a second impregnation tank treating fluid, wherein raw materials of the first impregnation tank treating fluid comprise aminopropyltrimethoxysilane and the like; the second impregnation tank treating fluid is prepared from the following raw materials: aminoethyl aminopropyl trimethoxy silane, vinyl propyl trimethoxy silane, 3-glycidyl oxypropyl trimethoxy silane and the like; and the third impregnation tank treating fluid is prepared from the following raw materials: styryl aminoethyl aminopropyl trimethoxy silane and the like. According to the invention, aminopropyltrimethoxysilane is used as a pre-impregnation treatment liquid, so that the surface tension of monofilaments of the dried glass fiber cloth is reduced in advance, and the glass fiber cloth can be more sufficiently impregnated by the treatment liquid in an impregnation tank 2; the three kinds of silane in the second impregnation tank are matched with one another to cope with most of compounding combination of downstream resin, the problem of matching with the downstream resin is solved, phenyl is introduced into styryl aminoethyl aminopropyl trimethoxy silane, and the heat resistance of the glass fiber cloth is further improved.

Description

Technical Field

[0001] The invention relates to an electronic-grade glass fiber cloth surface treatment agent for automobile plates and a preparation method thereof, belonging to the technical field of glass fiber cloth. Background Art

[0002] With the rapid development of new energy vehicles, the design of cars is changing rapidly. In summary, the direction of change is mainly in two aspects: electrification and intelligence. The penetration rate of new energy vehicles has reached 8%, and major manufacturers are increasing the research and application of intelligent software and hardware solutions. The entire automotive industry chain is facing upgrading and transformation. In this context, the proportion of electronic devices in the cost of automobiles will increase. It is expected that by 2030, the proportion of automotive electronic costs will be close to 50%. As the mother of electronics, PCB will also be significantly improved in its application in automobiles. According to CPCA, the global PCB output value will reach US$9.5 billion in 2025, and the compound growth rate from 2020 to 2025 will reach 7.8%. As the basic material of PCB boards, the application of glass fiber cloth will also grow rapidly, and the requirements for glass fiber cloth are also higher. Due to the special requirements of automotive PCB boards for safety, automotive boards, especially high-end new energy automotive PCB boards, have higher requirements for the stability, heat resistance, CAF resistance and other properties of glass fiber cloth. In order to seize market opportunities and improve the company's competitiveness, it is necessary to develop electronic-grade glass fiber cloth surface treatment agents for high-end automotive boards.

[0003] It is generally believed that the principle of surface treatment of glass fiber cloth by electronic grade glass fiber cloth surface treatment agent is: the silane hydrolyzate obtained after silane hydrolysis contains many silicon hydroxyl structures, which can undergo dehydration condensation with the silicon hydroxyl groups on the surface of glass cloth to form a stable Si-O-Si chemical bond, and the organic functional groups at the other end of the silane structure, such as amino and vinyl, can undergo chemical bonding with the organic functional groups on the resin to form a stable chemical bond. The silane surface treatment agent is the intermediate bridge for the combination of glass cloth and resin, and plays a very important role.

[0004] At present, the silane commonly used by various glass fiber cloth manufacturers is amino silane, and downstream manufacturers generally use epoxy resin or modified epoxy resin to match it. Subsequent PCB boards are mainly used in consumer electronics, home appliances and other fields. Based on the use environment, these fields do not have high requirements for the heat resistance and CAF resistance of the boards. Therefore, the glass fiber cloth with ordinary surface treatment process cannot meet the requirements of high-end automotive boards. Due to the strict requirements on safety for automobiles, especially new energy vehicles, the PCB boards have higher requirements on stability and reliability in use, so the heat resistance and CAF resistance of the boards are particularly high. Therefore, it is necessary to further optimize the existing glass fiber cloth surface treatment process.

[0005] At present, the conventional surface treatment method of glass fiber cloth is a single tank single treatment agent impregnation method. This impregnation method saves site space and is fast and efficient. However, the problem is that the post-processing line speed of glass fiber cloth is generally fast, and the impregnation is often not sufficient. In addition, the single silane impregnation is not compatible with the downstream resin. Now the downstream resin formula is no longer a single resin formula, but often a compound of multiple resins. Therefore, the single silane impregnated glass fiber cloth is not tightly combined with the downstream resin. Therefore, it is necessary to optimize and improve the glass fiber cloth surface treatment agent formula. In addition, the post-treatment process also has a significant impact on the impregnation effect of glass fiber cloth. At present, the drying of glass fiber cloth after impregnation is directly heated by gas furnace. This drying method is too intense and uneven, which can easily cause large differences in the impregnation of glass fiber cloth. Summary of the invention

[0006] The technical problem to be solved by the present invention is that the post-processing impregnation of the glass fiber cloth is not sufficient, the single silane impregnation used is not well matched with the downstream resin, and the bonding is not tight enough.

[0007] In order to solve the above problems, the present invention provides an electronic grade glass fiber cloth surface treatment agent for automobile panels, which comprises the following three impregnation tank treatment liquids which sequentially impregnate the glass fiber cloth:

[0008] No. 1 contains an immersion tank treatment solution, the raw materials of which include aminopropyltrimethoxysilane, a pH regulator, a surfactant and water;

[0009] No. 2 contains an immersion tank treatment solution, the raw materials of which include aminoethylaminopropyltrimethoxysilane, vinylpropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, a pH adjuster and water;

[0010] No. 3 contains an immersion tank treatment liquid, the raw materials of which include styrylaminoethylaminopropyltrimethoxysilane, a pH adjuster, a surfactant and water.

[0011] In the present invention, low-concentration aminopropyltrimethoxysilane is used as a pre-impregnation treatment liquid, and a surfactant is added. The main purpose is to reduce the surface tension of the dried glass fiber cloth monofilaments in advance, so that the treatment liquid in the second impregnation tank can more fully impregnate the glass fiber cloth. The low-concentration aminopropyltrimethoxysilane solution is used to pre-impregnate the glass fiber cloth, especially between the monofilaments of the glass fiber cloth. After pre-impregnation, the glass fiber cloth only passes through an extrusion wheel to squeeze out excess treatment liquid and water, and directly enters the second impregnation tank without drying. The second impregnation tank The three silanes are used as the main silanes. The combination of the three silanes can cope with most of the compound combinations of downstream resins. Among them, aminoethylaminopropyltrimethoxysilane can be combined with downstream epoxy resins, vinylpropyltrimethoxysilane can be combined with downstream vinyl resins, and 3-glycidyloxypropyltrimethoxysilane can be combined with downstream acrylic resins. Therefore, the combination of the three silanes can well solve the problem of matching with downstream resins. The main purpose of styrylaminoethylaminopropyltrimethoxysilane is to introduce phenyl to further improve the heat resistance of glass fiber cloth.

[0012] Preferably, the surfactant used in the No. 1 impregnation tank treatment liquid and the No. 3 impregnation tank treatment liquid is an anhydrous ethanol solution of a low-foaming surfactant. The surfactant can reduce the surface tension of the treatment liquid in the No. 1 impregnation tank, thereby reducing the surface tension of the glass fiber cloth after impregnation, especially the surface tension of the monofilament, which can provide favorable conditions for the full impregnation of the glass fiber cloth in the No. 2 impregnation tank. The structure of styrylaminoethylaminopropyltrimethoxysilane has a benzene ring and is not easy to hydrolyze. Adding a surfactant can promote hydrolysis.

[0013] Preferably, the No. 1 impregnation tank treatment liquid comprises, by mass percentage, 0.1% to 0.2% aminopropyltrimethoxysilane, 0.3% to 0.4% pH adjuster, 0.001% to 0.002% surfactant and the remainder water.

[0014] Preferably, the No. 2 impregnation tank treatment liquid comprises, by mass percentage, 0.4% to 0.5% aminoethylaminopropyltrimethoxysilane, 0.1% to 0.2% vinylpropyltrimethoxysilane, 0.1% to 0.2% 3-glycidyloxypropyltrimethoxysilane, 0.5% to 0.6% pH adjuster and the remainder water.

[0015] Preferably, the No. 3 impregnation tank treatment liquid comprises, by mass percentage, 0.1% to 0.2% of styrylaminoethylaminopropyltrimethoxysilane, 0.4% to 0.5% of a pH adjuster, 0.001% to 0.002% of a surfactant, and the remainder of water.

[0016] Preferably, the pH values ​​of the No. 1 impregnation tank treatment liquid, the No. 2 impregnation tank treatment liquid, and the No. 3 impregnation tank treatment liquid are adjusted to 3.0-4.0 by a pH adjuster. In the present invention, pure water is used as the silane hydrolysis environment, and the silane hydrolysis needs to be carried out in a weakly acidic environment.

[0017] More preferably, the pH adjuster is glacial acetic acid.

[0018] The present invention also provides a method for preparing the electronic-grade glass fiber cloth surface treatment agent for automobile panels, characterized in that the preparation method of the No. 1 impregnation tank treatment liquid is as follows: under stirring conditions, a pH regulator is added to water, and after mixing evenly, a surfactant is first added, and stirring is continued after the addition; aminopropyltrimethoxysilane is then added dropwise, and stirring is continued after the addition is completed until the solution is clear and transparent;

[0019] The preparation method of the No. 2 impregnation tank treatment liquid is as follows: adding a pH adjuster to water under stirring conditions, and then dropping aminoethylaminopropyltrimethoxysilane, vinylpropyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane in sequence after stirring, and continuing to stir after the dropping is completed until the solution is clear and transparent;

[0020] The preparation method of the No. 3 impregnation tank treatment liquid is as follows: adding a portion of water drops into styrylaminoethylaminopropyltrimethoxysilane, stirring while dropping, and continuing to stir after the dropping is completed to prepare a pre-hydrolysis liquid, which is sealed and stored at room temperature; adding a pH regulator and a surfactant to the remaining water under stirring, stirring, and then dropping the pre-hydrolysis liquid, and continuing to stir after the dropping is completed until the solution is clear and transparent.

[0021] Preferably, the preparation method of the No. 1 impregnation tank treatment liquid is as follows: under stirring conditions, a pH regulator is added to water, and after mixing evenly, a surfactant is first added, and stirring is continued for 10 minutes after the addition; aminopropyltrimethoxysilane is then added dropwise, and stirring is continued for at least 30 minutes after the addition is completed, until the solution becomes clear and transparent;

[0022] The preparation method of the No. 2 impregnation tank treatment liquid is as follows: a pH regulator is added to water under stirring conditions, and after stirring for 15 minutes, aminoethylaminopropyltrimethoxysilane, vinylpropyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane are added dropwise in sequence, and after the addition is completed, stirring is continued for at least 30 minutes until the solution becomes clear and transparent;

[0023] The preparation method of the No. 3 impregnation tank treatment liquid is as follows: adding a portion of water drops into styrylaminoethylaminopropyltrimethoxysilane, stirring while dropping, and continuing to stir for 30 minutes after the dropwise addition is completed to prepare a pre-hydrolysis liquid, which is sealed and stored at room temperature for at least 48 hours; adding a pH regulator and a surfactant to the remaining water under stirring conditions, stirring for 15 minutes, and then dropping the pre-hydrolysis liquid, and continuing to stir for at least 30 minutes after the dropwise addition is completed until the solution is clear and transparent.

[0024] Preferably, in the pre-hydrolysis solution, the mass ratio of styrylaminoethylaminopropyltrimethoxysilane to water is 20:1.

[0025] Compared with the prior art, the present invention has the following technical effects:

[0026] (1) In the present invention, the glass fiber cloth is pre-impregnated with the treatment liquid in the impregnation tank to reduce the surface tension of the glass fiber cloth entering the impregnation tank after drying, and a surfactant is added to reduce the surface tension of the entire treatment liquid, so that the surface of the glass fiber cloth can be fully impregnated, especially the difficult-to-impregnate area between the monofilaments of the glass fiber cloth, which is the main reason for the abnormal heat resistance and CAF resistance of most glass fiber cloth boards;

[0027] (2) In the present invention, the treatment liquid in the second impregnation tank is used as the main treatment liquid, and three silanes are used for compounding, which can fully match the downstream resin and combine more closely with the downstream resin. The glass fiber cloth comes out of the first impregnation tank, and only passes through the extrusion wheel to squeeze out the excess treatment liquid on the surface of the glass fiber cloth without drying, and directly enters the second impregnation tank. The glass fiber cloth with reduced surface tension enters the second impregnation tank, and the treatment liquid can more fully infiltrate the glass fiber cloth;

[0028] (3) In the present invention, the styrylaminoethylaminopropyltrimethoxysilane in the No. 3 impregnation tank contains a benzene ring, which can further improve the heat resistance of the glass fiber cloth. DETAILED DESCRIPTION

[0029] In order to make the present invention more clearly understood, preferred embodiments are described in detail as follows.

[0030] Example 1

[0031] An electronic grade glass fiber cloth surface treatment agent for automobile panels, the formula and preparation method thereof are as follows:

[0032] 1) No. 1 impregnation tank treatment liquid

[0033] Raw materials: 1 part by weight of aminopropyltrimethoxysilane, 4 parts by weight of glacial acetic acid, 0.3 parts by weight of anhydrous ethanol solution of a low-foaming surfactant, and 1000 parts by weight of pure water.

[0034] Preparation method: Add glacial acetic acid to pure water under stirring conditions, mix well, first add anhydrous ethanol solution of low-foaming surfactant, and continue stirring for 10 minutes after adding; then add aminopropyltrimethoxysilane dropwise, and continue stirring for at least 30 minutes after the addition is completed, until the solution is clear and transparent.

[0035] 2) No. 2 impregnation tank treatment liquid

[0036] Raw materials: 4 parts by weight of aminoethylaminopropyltrimethoxysilane, 1 part by weight of vinylpropyltrimethoxysilane, 1 part by weight of 3-glycidyloxypropyltrimethoxysilane, 6 parts by weight of glacial acetic acid, and 1000 parts by weight of pure water;

[0037] Preparation method: Add glacial acetic acid to pure water under stirring conditions, stir for 15 minutes, then add aminoethylaminopropyltrimethoxysilane, vinylpropyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane dropwise in sequence. After the addition is complete, continue stirring for at least 30 minutes until the solution becomes clear.

[0038] 3) No. 3 impregnation tank treatment liquid

[0039] Raw materials: 1 part by weight of styrylaminoethylaminopropyltrimethoxysilane, 4 parts by weight of glacial acetic acid, 0.3 parts by weight of anhydrous ethanol solution of a low-foaming surfactant, and 1000 parts by weight of pure water.

[0040] Preparation method: Add part of the pure water dropwise into styrylaminoethylaminopropyltrimethoxysilane, stirring while adding dropwise, and continue stirring for 30 minutes after the addition is completed to prepare a pre-hydrolysis solution (wherein the mass ratio of styrylaminoethylaminopropyltrimethoxysilane to water is 20:1), which is sealed and stored at room temperature for at least 48 hours; under stirring conditions, add glacial acetic acid and anhydrous ethanol solution of a low-foaming surfactant to the remaining pure water, stir for 15 minutes, and then add the pre-hydrolysis solution dropwise. After the addition is completed, continue stirring for at least 30 minutes until the solution becomes clear and transparent.

[0041] A method for treating electronic-grade glass fiber cloth for automobile panels: first, put the glass fiber cloth into No. 1 impregnation tank containing No. 1 impregnation tank treatment liquid for impregnation for 1 second; take out the glass fiber cloth without drying and directly put it into No. 2 impregnation tank containing No. 2 impregnation tank treatment liquid for impregnation for 2 seconds; take out the glass fiber cloth without drying and directly put it into No. 3 impregnation tank containing No. 3 impregnation tank treatment liquid for impregnation for 1 second; after taking out, dry it with hot air at 100°C for 20 seconds. The gas combustion direct drying of the original impregnation drying furnace is changed to hot air drying, which makes the drying more uniform and gentle, thereby facilitating further improving the impregnation property of the glass fiber cloth.

[0042] The above treatment method is suitable for the surface treatment of glass fiber cloths such as 1080 and 2116.

[0043] Example 2

[0044] The difference between this embodiment and embodiment 1 is that the anhydrous ethanol solution of the low-foaming surfactant is replaced by a conventional surfactant: a non-ionic polyether surfactant.

[0045] The method for treating the electronic-grade glass fiber cloth for automobile panels of this embodiment will generate a lot of foam during the process.

[0046] Comparative Example 1

[0047] The difference between this comparative example and Example 1 is that no surfactant is added to the treatment liquid in No. 1 impregnation tank and the treatment liquid in No. 3 impregnation tank.

[0048] Comparative Example 2

[0049] The difference between this comparative example and Example 1 is that: the No. 1 impregnation tank treatment liquid is not used, and only the No. 2 impregnation tank treatment liquid and the No. 3 impregnation tank treatment liquid are used for treatment.

[0050] Comparative Example 3

[0051] The difference between this comparative example and Example 1 is that: No. 1 impregnation tank treatment liquid and No. 3 impregnation tank treatment liquid are not used, and only No. 2 impregnation tank treatment liquid is used for treatment.

[0052] Relevant tests were performed on the glass fiber cloths treated by Examples 1-2 and Comparative Examples 1-2.

[0053] 1. The glass fiber cloth treated by Example 1-2 and Comparative Example 1-2 was subjected to an impregnation test. The test results are shown in Table 1.

[0054] Table 1

[0055]

[0056]

[0057] As can be seen from Table 1, the glass fiber cloth treated in Example 1 has the best impregnation property.

[0058] 2. The heat resistance of the plates obtained by downstream treatment of the glass fiber cloth treated in Example 1-2 and Comparative Example 1-2 is tested, and the test results are shown in Table 2. Test conditions: in a bias voltage of 100V, 85°C, 85% RH environment, after continuous placement for 1000 hours.

[0059] Table 2

[0060]

[0061] As can be seen from Table 2, the board prepared from the glass fiber cloth treated in Example 1 has the best heat resistance.

[0062] 3. The PCB boards obtained by downstream treatment of the glass fiber cloth treated in Example 1-2 and Comparative Example 1-2 were subjected to CAF resistance test, and the test results are shown in Table 3. Test conditions: in a bias voltage of 100V, 85°C, 85% RH environment, and tested after continuous placement for 1000 hours.

[0063] Table 3

[0064]

[0065] As can be seen from Table 3, the PCB board prepared from the glass fiber cloth treated in Example 1 has the best CAF resistance.

[0066] In summary, the glass fiber cloth treated with the electronic-grade glass fiber cloth surface treatment agent provided by the present invention has better impregnation, heat resistance and PCB CAF resistance, and can significantly improve product quality.

Claims

1. A surface treatment agent for electronic grade glass fiber cloth for automobile panels, characterized in that: The invention comprises the following three impregnation tank treatment liquids which sequentially impregnate the glass fiber cloth: No. 1 contains an immersion tank treatment solution, the raw materials of which include aminopropyltrimethoxysilane, a pH regulator, a surfactant and water; No. 2 contains an immersion tank treatment solution, the raw materials of which include aminoethylaminopropyltrimethoxysilane, vinylpropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, a pH adjuster and water; No. 3 contains an immersion tank treatment liquid, the raw materials of which include styrylaminoethylaminopropyltrimethoxysilane, a pH adjuster, a surfactant and water.

2. The surface treatment agent for electronic grade glass fiber cloth for automobile plate according to claim 1, characterized in that: The surfactant used in the No. 1 impregnation tank treatment liquid and the No. 3 impregnation tank treatment liquid is an anhydrous ethanol solution of a low-foaming surfactant.

3. The surface treatment agent for electronic grade glass fiber cloth for automobile plate according to claim 1, characterized in that: The No. 1 impregnation tank treatment liquid comprises, by mass percentage, 0.1% to 0.2% aminopropyltrimethoxysilane, 0.3% to 0.4% pH regulator, 0.001% to 0.002% surfactant and the balance water.

4. The surface treatment agent for electronic grade glass fiber cloth for automobile plate according to claim 1, characterized in that: The No. 2 impregnation tank treatment liquid comprises, by mass percentage, 0.4% to 0.5% aminoethylaminopropyltrimethoxysilane, 0.1% to 0.2% vinylpropyltrimethoxysilane, 0.1% to 0.2% 3-glycidyloxypropyltrimethoxysilane, 0.5% to 0.6% pH regulator and the remainder water.

5. The surface treatment agent for electronic grade glass fiber cloth for automobile plate according to claim 1, characterized in that: The No. 3 impregnation tank treatment liquid comprises raw materials including, by mass percentage, 0.1% to 0.2% of styrylaminoethylaminopropyltrimethoxysilane, 0.4% to 0.5% of a pH regulator, 0.001% to 0.002% of a surfactant, and the balance of water.

6. The surface treatment agent for electronic grade glass fiber cloth for automobile plate according to any one of claims 1 to 5, characterized in that: The pH values ​​of the No. 1 impregnation tank treatment liquid, the No. 2 impregnation tank treatment liquid, and the No. 3 impregnation tank treatment liquid are adjusted to 3.0 to 4.0 by a pH adjuster.

7. The surface treatment agent for electronic grade glass fiber cloth for automobile plate according to claim 6, characterized in that: The pH regulator is glacial acetic acid.

8. The method for preparing the surface treatment agent for electronic grade glass fiber cloth for automobile plate according to any one of claims 1 to 7, characterized in that: The preparation method of the No. 1 impregnation tank treatment liquid is as follows: adding a pH regulator to water under stirring conditions, mixing evenly, first adding a surfactant, and continuing to stir after adding; then dropping aminopropyltrimethoxysilane, and continuing to stir after the dropping is complete until the solution is clear and transparent; The preparation method of the No. 2 impregnation tank treatment liquid is as follows: adding a pH adjuster to water under stirring conditions, and then dropping aminoethylaminopropyltrimethoxysilane, vinylpropyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane in sequence after stirring, and continuing to stir after the dropping is completed until the solution is clear and transparent; The preparation method of the No. 3 impregnation tank treatment liquid is as follows: adding a portion of water drops into styrylaminoethylaminopropyltrimethoxysilane, stirring while dropping, and continuing to stir after the dropping is completed to prepare a pre-hydrolysis liquid, which is sealed and stored at room temperature; adding a pH regulator and a surfactant to the remaining water under stirring, stirring, and then dropping the pre-hydrolysis liquid, and continuing to stir after the dropping is completed until the solution is clear and transparent.

9. The method for preparing the surface treatment agent for electronic grade glass fiber cloth for automobile plate according to claim 8, characterized in that: The preparation method of the No. 1 impregnation tank treatment liquid is as follows: under stirring conditions, a pH regulator is added to water, and after mixing evenly, a surfactant is first added, and stirring is continued for 10 minutes after the addition; aminopropyltrimethoxysilane is then added dropwise, and stirring is continued for at least 30 minutes after the addition is completed, until the solution becomes clear and transparent; The preparation method of the No. 2 impregnation tank treatment liquid is as follows: a pH regulator is added to water under stirring conditions, and after stirring for 15 minutes, aminoethylaminopropyltrimethoxysilane, vinylpropyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane are added dropwise in sequence, and after the addition is completed, stirring is continued for at least 30 minutes until the solution becomes clear and transparent; The preparation method of the No. 3 impregnation tank treatment liquid is as follows: adding a portion of water drops into styrylaminoethylaminopropyltrimethoxysilane, stirring while dropping, and continuing to stir for 30 minutes after the dropwise addition is completed to prepare a pre-hydrolysis liquid, which is sealed and stored at room temperature for at least 48 hours; adding a pH regulator and a surfactant to the remaining water under stirring conditions, stirring for 15 minutes, and then dropping the pre-hydrolysis liquid, and continuing to stir for at least 30 minutes after the dropwise addition is completed until the solution is clear and transparent.

10. The method for preparing the surface treatment agent for electronic grade glass fiber cloth for automobile plate according to claim 8 or 9, characterized in that: In the pre-hydrolysis solution, the mass ratio of styrylaminoethylaminopropyltrimethoxysilane to water is 20:1.

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