A surface treatment agent for electronic-grade fiberglass cloth and its preparation method

Abstract

The present invention provides a surface treatment agent for electronic-grade fiberglass cloth, which is made from the following raw materials in parts by weight: 2-3 parts of a modifier, 4-5 parts of a dispersant, 6-9 parts of a co-solvent, and 88-92 parts of water. The present invention also provides a preparation method of the surface treatment agent for electronic-grade fiberglass cloth. The surface treatment agent provided by the present invention can effectively improve the water resistance, heat resistance of the electronic-grade fiberglass cloth and the bonding force between it and the resin.

Description

Technical Field

[0001] The present invention relates to a surface treatment agent, in particular to a surface treatment agent for electronic-grade glass fiber cloth and a preparation method thereof. Background Art

[0002] Electronic-grade glass fiber cloth is prepared from electronic-grade glass fiber yarns through warping, sizing, weaving, desizing, and chemical treatment, and is mainly used for the manufacture of copper-clad laminates, which are the special basic materials for printed circuit boards (PCBs). Electronic-grade glass fiber cloth itself cannot be directly used for the printing of circuit boards. It needs to be combined with resin adhesive to form a prepreg, and then pressed with copper foil to make a copper-clad laminate, and finally used for the printing of circuit boards. However, pure glass fiber cloth belongs to inorganic fiber, while resin belongs to organic matter, and the compatibility and binding between the two are not good. Therefore, it usually needs to be surface-treated. Although some surface treatment agents in the prior art can improve this point, the surface treatment effect is general, and the water resistance and heat resistance of the treated electronic-grade glass fiber cloth are not good. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a surface treatment agent for electronic-grade glass fiber cloth, which can effectively improve the water resistance, heat resistance of the electronic-grade glass fiber cloth and its bonding force with resin.

[0004] To solve the above technical problem, the technical solution of the present invention is:

[0005] A surface treatment agent for electronic-grade glass fiber cloth is made from the following raw materials in parts by weight: 2-3 parts of modifier, 4-5 parts of dispersant, 6-9 parts of cosolvent, and 88-92 parts of water.

[0006] Further, the modifier in the present invention is 10-(meth)acryloyloxy decyl phosphate.

[0007] Further, the dispersant in the present invention is prepared by the following steps:

[0008] Sodium 3-chloro-2-hydroxypropane sulfonate is added to dimethyl sulfoxide and mixed evenly to obtain solution A, tributyltriphenylphosphonium bromide is added to dimethyl sulfoxide and mixed evenly to obtain solution B, solution A and solution B are mixed and magnetically stirred for 4-6 hours to obtain a mixed solution, and the mixed solution is allowed to stand for 1-2 hours to be layered, and then the lower layer liquid is taken out to obtain the dispersant.

[0009] Further, in step (1) of the present invention, the ratio of sodium 3-chloro-2-hydroxypropane sulfonate to dimethyl sulfoxide in solution A is 0.6 mol:1 L, the ratio of tributyltriphenylphosphonium bromide to dimethyl sulfoxide in solution B is 0.5 mol:1 L, and the volume ratio of solution A to solution B is 1:1.

[0010] Furthermore, the cosolvent in the present invention is N,N-dimethylformamide.

[0011] Furthermore, the water in the present invention is pure water.

[0012] Another technical problem to be solved by the present invention is to provide a preparation method of the above surface treatment agent for electronic glass fiber cloth.

[0013] To solve the above technical problems, the technical solution is as follows:

[0014] A preparation method of a surface treatment agent for electronic glass fiber cloth includes the following steps:

[0015] S1. Weigh each raw material by weight parts, add the modifier and the cosolvent to 1 / 4 of the weight of water, and stir for 20 - 30 minutes to obtain a first mixed solution.

[0016] S2. Add the dispersant to the remaining water, and stir for 10 - 20 minutes to obtain a second mixed solution.

[0017] S3. Mix the first mixed solution obtained in step S1 and the second mixed solution obtained in step S2, and stir for 30 - 40 minutes to obtain a surface treatment agent for electronic glass fiber cloth.

[0018] Furthermore, in step S1 of the present invention, the stirring speed is 300 revolutions per minute.

[0019] Furthermore, in step S2 of the present invention, the stirring speed is 100 revolutions per minute.

[0020] Furthermore, in step S3 of the present invention, the stirring speed is 200 revolutions per minute.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The modifier used in the present invention, 10-(meth)acryloyloxydecyl phosphate, can improve the compatibility between the electronic glass fiber cloth and the resin, enhance the bonding force between the electronic glass fiber cloth and the resin, reduce the water absorption rate of the electronic glass fiber cloth, and improve the water resistance of the electronic glass fiber cloth.

[0023] (2) The present invention also uses a dispersant prepared by mixing and reacting sodium 3-chloro-2-hydroxypropanesulfonate and butyltriphenylphosphonium bromide. This dispersant can improve the coating uniformity of the surface treatment agent on the electronic glass fiber cloth, thereby improving the heat resistance of the electronic fiber cloth and further enhancing the bonding force between the electronic glass fiber cloth and the resin. Detailed Embodiments

[0024] The present invention will be described in detail below in conjunction with specific embodiments. The illustrative embodiments of the present invention and their descriptions are used to explain the present invention, but do not limit the present invention.

[0025] Example 1

[0026] The surface treatment agent for electronic grade fiberglass cloth is made from the following raw materials in parts by weight: 2.5 parts of 10-(meth)acryloyloxy decyl phosphate, 4.5 parts of dispersant, 8 parts of N,N-dimethylformamide, and 90 parts of pure water.

[0027] Among them, the dispersant is made by the following steps:

[0028] Sodium 3-chloro-2-hydroxypropanesulfonate is added to dimethyl sulfoxide according to the ratio of 0.6 mol:1 L and mixed evenly to obtain solution A. Butyl triphenylphosphonium bromide is added to dimethyl sulfoxide according to the ratio of 0.5 mol:1 L and mixed evenly to obtain solution B. Solution A and solution B with a volume ratio of 1:1 are mixed and magnetically stirred for 5 hours to obtain a mixed solution. The mixed solution is allowed to stand for 1.5 hours and stratified, and then the lower layer liquid is taken out to obtain the dispersant.

[0029] The preparation method of Example 1 includes the following steps:

[0030] S1. Weigh each raw material according to the parts by weight. Add 10-(meth)acryloyloxy decyl phosphate and N,N-dimethylformamide to 1 / 4 of the weight of pure water, and stir at a speed of 300 revolutions per minute for 25 minutes to obtain a mixed solution 1;

[0031] S2. Add the dispersant to the remaining pure water, and stir at a speed of 100 revolutions per minute for 15 minutes to obtain a mixed solution 2;

[0032] S3. Mix the mixed solution 1 obtained in step S1 and the mixed solution 2 obtained in step S2, and stir at a speed of 200 revolutions per minute for 35 minutes to obtain the surface treatment agent for electronic grade fiberglass cloth.

[0033] Example 2

[0034] The surface treatment agent for electronic grade fiberglass cloth is made from the following raw materials in parts by weight: 2 parts of 10-(meth)acryloyloxy decyl phosphate, 4 parts of dispersant, 6 parts of N,N-dimethylformamide, and 88 parts of pure water.

[0035] Among them, the dispersant is made by the following steps:

[0036] Sodium 3-chloro-2-hydroxypropanesulfonate was added to dimethyl sulfoxide in a ratio of 0.6 mol:1 L and mixed evenly to obtain solution A. Tetrabutylphosphonium bromide was added to dimethyl sulfoxide in a ratio of 0.5 mol:1 L and mixed evenly to obtain solution B. Solution A and solution B with a volume ratio of 1:1 were mixed and stirred magnetically for 4 hours to obtain a mixed solution. The mixed solution was allowed to stand for 1 hour to separate layers, and the lower layer liquid was taken out to obtain a dispersant.

[0037] The preparation method of Example 2 includes the following steps:

[0038] S1. Weigh each raw material by weight. Add 10-(meth)acryloyloxydecyl phosphate and N,N-dimethylformamide to 1 / 4 weight of pure water, and stir at a speed of 300 revolutions per minute for 20 minutes to obtain mixture 1.

[0039] S2. Add the dispersant to the remaining pure water, and stir at a speed of 100 revolutions per minute for 10 minutes to obtain mixture 2.

[0040] S3. Mix mixture 1 obtained in step S1 and mixture 2 obtained in step S2, and stir at a speed of 200 revolutions per minute for 30 minutes to obtain a surface treatment agent for electronic-grade fiberglass cloth.

[0041] Example 3

[0042] The surface treatment agent for electronic-grade fiberglass cloth is made of the following raw materials by weight: 2.5 parts of 10-(meth)acryloyloxydecyl phosphate, 4 parts of dispersant, 7 parts of N,N-dimethylformamide, and 91 parts of pure water.

[0043] Among them, the dispersant is made by the following steps:

[0044] Sodium 3-chloro-2-hydroxypropanesulfonate was added to dimethyl sulfoxide in a ratio of 0.6 mol:1 L and mixed evenly to obtain solution A. Tetrabutylphosphonium bromide was added to dimethyl sulfoxide in a ratio of 0.5 mol:1 L and mixed evenly to obtain solution B. Solution A and solution B with a volume ratio of 1:1 were mixed and stirred magnetically for 4.5 hours to obtain a mixed solution. The mixed solution was allowed to stand for 2 hours to separate layers, and the lower layer liquid was taken out to obtain a dispersant.

[0045] The preparation method of Example 3 includes the following steps:

[0046] S1. Weigh each raw material by weight. Add 10-(meth)acryloyloxydecyl phosphate and N,N-dimethylformamide to 1 / 4 weight of pure water, and stir at a speed of 300 revolutions per minute for 24 minutes to obtain mixture 1.

[0047] S2. Add the dispersant to the remaining pure water, and stir at a speed of 100 revolutions per minute for 18 minutes to obtain mixture 2.

[0048] S3. Mix the first mixture obtained in step S1 and the second mixture obtained in step S2, and stir at a speed of 200 revolutions per minute for 32 minutes to obtain a surface treatment agent for electronic glass fiber cloth.

[0049] Example 4

[0050] The surface treatment agent for electronic glass fiber cloth is made from the following raw materials by weight: 3 parts of 10-(meth)acryloyloxy decyl phosphate, 5 parts of dispersant, 9 parts of N,N-dimethylformamide, and 92 parts of pure water.

[0051] Among them, the dispersant is made by the following steps:

[0052] Sodium 3-chloro-2-hydroxypropane sulfonate is added to dimethyl sulfoxide according to the ratio of 0.6 mol:1 L and mixed evenly to obtain solution A. Tetrabutylphosphonium bromide is added to dimethyl sulfoxide according to the ratio of 0.5 mol:1 L and mixed evenly to obtain solution B. Solution A and solution B with a volume ratio of 1:1 are mixed and stirred magnetically for 6 hours to obtain a mixture. The mixture is allowed to stand for 2 hours and the lower layer liquid is taken out to obtain the dispersant.

[0053] The preparation method of Example 4 includes the following steps:

[0054] S1. Weigh each raw material according to the weight parts. Add 10-(meth)acryloyloxy decyl phosphate and N,N-dimethylformamide to 1 / 4 of the weight of pure water, and stir at a speed of 300 revolutions per minute for 30 minutes to obtain the first mixture;

[0055] S2. Add the dispersant to the remaining pure water, and stir at a speed of 100 revolutions per minute for 20 minutes to obtain the second mixture;

[0056] S3. Mix the first mixture obtained in step S1 and the second mixture obtained in step S2, and stir at a speed of 200 revolutions per minute for 40 minutes to obtain a surface treatment agent for electronic glass fiber cloth.

[0057] Comparative Example 1

[0058] The difference from Example 1 is that the raw materials do not include 10-(meth)acryloyloxy decyl phosphate.

[0059] Comparative Example 2

[0060] The difference from Example 1 is that the raw materials do not include the dispersant, and the preparation step of the dispersant is omitted.

[0061] Experimental Example:

[0062] After desizing the E-grade electronic glass fiber cloth, it was impregnated in a surface treatment agent (Examples 1-4, Comparative Examples 1-2) and dried at 80 °C to obtain a pretreated electronic glass fiber cloth.

[0063] By weight, 75 parts of epoxy resin E-44, 2.5 parts of dicyandiamide, 0.1 part of dimethylimidazole, 28 parts of talc powder, and 70 parts of N,N-dimethylformamide were mixed and stirred evenly to obtain a resin sizing solution. The pretreated electronic glass fiber cloth was impregnated in the resin sizing solution and dried at 130 °C for 15 minutes to obtain a prepreg with an average thickness of 50 μm.

[0064] Four prepregs were laminated, and copper foils with a thickness of 18 μm were covered on the upper and lower sides respectively. Then they were placed in a hot press and hot-pressed at 2 MPa and 200 °C for 2 hours to obtain a copper clad laminate with a thickness of 0.2 mm.

[0065] Test Example 1:

[0066] Using a laser drilling machine, blind holes with a bottom diameter of 60 μm and a top diameter of 70 μm were drilled in the prepregs prepared in the experimental examples (Examples 1-4, Comparative Examples 1-2). The energy during drilling was 2 mJ, the pulse width was 4 μs, and the number of irradiations was 3 times. After decontaminating the blind holes, the blind holes were observed with a scanning electron microscope, and the maximum value Lm of the residual length of the glass fibers on the side wall of the blind hole in the horizontal direction was measured. The smaller Lm is, the better the bonding strength between the electronic glass fiber and the resin. The test results are shown in Table 1:

[0067] Lm (μm) Example 1 4 Example 2 6 Example 3 3 Example 4 5 Comparative Example 1 11 Comparative Example 2 9

[0068] Table 1

[0069] As can be seen from Table 1, the Lm values of Examples 1-4 of the present invention are all smaller, indicating that the present invention can effectively improve the bonding strength between the electronic glass fiber cloth and the resin. The partial raw materials and preparation steps used in Comparative Examples 1 and 2 are different from those in Example 1. Compared with Example 1, the Lm values of Comparative Examples 1 and 2 have all increased, indicating that both 10-(meth)acryloyloxydecyl phosphate and the dispersant used in the present invention can effectively improve the bonding strength between the electronic glass fiber cloth and the resin.

[0070] Test Example 2:

[0071] Referring to the IPC-TM-650 2.6 standard, the water absorption rate of the copper clad laminates prepared in the experimental examples (Examples 1-4, Comparative Example 1) was tested. The lower the water absorption rate, the better the water resistance. The test results are shown in Table 2:

[0072]

[0073]

[0074] Table 2

[0075] As can be seen from Table 2, the water absorption rates of Examples 1-4 of the present invention are all relatively low, indicating that the present invention can effectively improve the water resistance of the electronic grade glass fiber cloth and the copper clad laminate. Some of the raw materials used in Comparative Example 1 are different from those in Example 1. Compared with Example 1, the water absorption rate of Comparative Example 1 increases significantly, indicating that the 10-(meth)acryloyloxy decyl phosphate used in the present invention can effectively improve the water resistance of the electronic grade glass fiber cloth and the copper clad laminate.

[0076] Test Example Three:

[0077] Referring to GB / T 36800.1-2018 Plastics - Thermomechanical analysis (TMA) - Part 1, the glass transition temperatures of the copper clad laminates (Examples 1-4, Comparative Example 2) prepared in the experimental examples were tested. The higher the glass transition temperature, the better the heat resistance. The test results are shown in Table 3:

[0078] Glass transition temperature (°C) Example 1 175 Example 2 172 Example 3 177 Example 4 174 Comparative Example 2 161

[0079] Table 3

[0080] As can be seen from Table 3, the glass transition temperatures of Examples 1-4 of the present invention are all relatively high, indicating that the present invention can effectively improve the heat resistance of the electronic grade glass fiber cloth and the copper clad laminate. Some of the raw materials and preparation steps used in Comparative Example 2 are different from those in Example 1. Compared with Example 1, the glass transition temperature of Comparative Example 2 decreases significantly, indicating that the dispersant used in the present invention can effectively improve the heat resistance of the electronic grade glass fiber cloth and the copper clad laminate.

[0081] The above embodiments are only illustrative of the principles and effects of the present invention, and are not used to limit the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A surface treatment agent for electronic-grade fiberglass cloth, characterized in that: It is made from the following raw materials in parts by weight: 2 - 3 parts of modifier, 4 - 5 parts of dispersant, 6 - 9 parts of cosolvent, and 88 - 92 parts of water. The modifier is 10-(meth)acryloyloxy decyl phosphate; the dispersant is made by the following steps: Add sodium 3-chloro-2-hydroxypropane sulfonate to dimethyl sulfoxide and mix evenly to obtain solution A. Add butyl triphenyl phosphonium bromide to dimethyl sulfoxide and mix evenly to obtain solution B. Mix solution A and solution B, and stir magnetically for 4 - 6 hours to obtain a mixed solution. Let the mixed solution stand for 1 - 2 hours to separate layers, and then take out the lower layer liquid to obtain the dispersant.

2. The surface treatment agent for electronic-grade fiberglass cloth according to claim 1, wherein: In the above steps, the ratio of sodium 3-chloro-2-hydroxypropane sulfonate to dimethyl sulfoxide in solution A is 0.6 mol:1 L, the ratio of butyl triphenyl phosphonium bromide to dimethyl sulfoxide in solution B is 0.5 mol:1 L, and the volume ratio of solution A to solution B is 1:

1.

3. The surface treatment agent for electronic grade fiberglass cloth according to claim 1, characterized in that: The cosolvent is N,N-dimethylformamide.

4. The surface treatment agent for electronic glass fiber cloth according to claim 1, characterized in that: The water is pure water.

5. The preparation method of a surface treatment agent for electronic glass fiber cloth according to any one of claims 1 to 4, characterized in that: It includes the following steps: S1. Weigh each raw material according to the parts by weight. Add the modifier and cosolvent to 1 / 4 of the weight of water, and stir for 20 - 30 minutes to obtain mixture 1. S2. Add the dispersant to the remaining water, and stir for 10 - 20 minutes to obtain mixture 2. S3. Mix mixture 1 obtained in step S1 and mixture 2 obtained in step S2, and stir for 30 - 40 minutes to obtain a surface treatment agent for electronic grade glass fiber cloth.

6. The preparation method of a surface treatment agent for electronic-grade fiberglass cloth according to claim 5, characterized in that: In step S1, the stirring speed is 300 revolutions per minute.

7. The preparation method of a surface treatment agent for electronic glass fiber cloth according to claim 5, characterized in that: In step S2, the stirring speed is 100 revolutions per minute.

8. The preparation method of a surface treatment agent for electronic-grade fiberglass cloth according to claim 5, wherein: In step S3, the stirring speed is 200 revolutions per minute.

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