A sizing agent for electronic grade glass fiber cloth and preparation method thereof

Abstract

The present invention provides a sizing agent for electronic-grade glass fiber cloth, which is made of the following raw materials in parts by weight: 3-6 parts of a film-forming agent, 0.5-1 parts of guar gum, 0.6-0.9 parts of an emulsifier, 1-1.5 parts of an auxiliary agent, 1.5-2 parts of a reinforcing agent, 2-3 parts of a lubricant, and 82-85 parts of deionized water. The present invention also provides a preparation method of the sizing agent. The sizing agent for electronic-grade glass fiber cloth provided by the present invention can effectively reduce the hairiness of the electronic-grade glass fiber cloth and can also improve the mechanical properties and wear resistance of the electronic-grade glass fiber cloth.

Description

Technical Field

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

[0002] Electronic-grade glass fiber cloth is woven from electronic-grade glass fiber yarn and is primarily used in the manufacture of copper-clad laminates (CCLs), the specialized base material for printed circuit boards (PCBs). The quality of electronic-grade glass fiber cloth is a key factor influencing the appearance, processing performance, and physical and chemical properties of the CCLs. As printed circuit board manufacturing technology evolves toward micro-apertures, fine lines, high-density wiring, and multiple layers, requirements for substrates such as heat resistance, low coefficient of expansion, high dimensional stability, and low dielectric loss are constantly increasing. Consequently, the hairiness of electronic-grade glass fiber cloth, resin impregnation, and the strength and heat resistance of the board have become key concerns for CCLs.

[0003] Sizing is a key step in the glass fiber cloth processing process. This step involves applying a thin sizing film to the surface of the glass fiber cloth to improve fiber bundling, reduce the friction coefficient of the glass fiber filaments, and enhance the mechanical and wear resistance of the glass fiber, making it more flexible and resistant to mechanical damage. Existing sizing agents for electronic-grade glass fiber cloth have various problems, including a high hairiness after sizing and limited improvement in mechanical and wear resistance properties. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a sizing agent for electronic-grade glass fiber cloth, which can effectively reduce the hairiness of the electronic-grade glass fiber cloth and improve the mechanical properties and wear resistance of the electronic-grade glass fiber cloth.

[0005] In order to solve the above technical problems, the technical solution of the present invention is:

[0006] A sizing agent for electronic-grade glass fiber cloth is prepared from the following raw materials in parts by weight: 3-6 parts of a film-forming agent, 0.5-1 part of guar gum, 0.6-0.9 parts of an emulsifier, 1-1.5 parts of an auxiliary agent, 1.5-2 parts of a reinforcing agent, 2-3 parts of a lubricant, and 82-85 parts of deionized water.

[0007] Furthermore, the film-forming agent of the present invention is composed of carboxymethyl starch and polyvinyl alcohol 17-99 in a weight ratio of 2:1.

[0008] Furthermore, the emulsifier of the present invention is dodecylphenol polyoxyethylene ether.

[0009] Furthermore, the auxiliary agent of the present invention is methyl glucose polyoxypropylene ether distearate.

[0010] Furthermore, the reinforcing agent of the present invention is prepared by the following steps:

[0011] (1) Add erbium oxide to deionized water, heat to 45°C, start stirring, add concentrated hydrochloric acid, and stir for 30 minutes to obtain an erbium chloride solution;

[0012] (2) dissolving tetradecanoic acid in deionized water, stirring for 10 minutes, adding a sodium hydroxide aqueous solution, heating to 90° C. and continuing to stir for 20 minutes, adjusting the pH value to 7, adding the erbium chloride solution obtained in step (1), continuing to stir at 90° C. for 2 hours, and then standing to separate into an aqueous phase and an oil phase, discarding the aqueous phase, washing the oil phase with deionized water three times, and then filtering to obtain a filter cake, placing the filter cake in an oven and drying it to a constant weight to obtain a modifier;

[0013] (3) The modifier obtained in step (2) is added to an ethanol aqueous solution, and the mixture is stirred for 10 minutes to obtain a modifier solution. Aluminum silicate is added to the modifier solution and the mixture is stirred for 12 hours to obtain a reaction solution. The reaction solution is filtered to obtain a filter cake. The filter cake is washed three times with deionized water and anhydrous ethanol, respectively, and then dried in an oven to a constant weight to obtain a reinforcing agent.

[0014] Furthermore, in step (1) of the present invention, the mass concentration of concentrated hydrochloric acid is 38%, the weight ratio of erbium oxide, deionized water, and concentrated hydrochloric acid is 1:10:3, and the stirring speed is 200 rpm; in step (2), the mass concentration of sodium hydroxide aqueous solution is 0.5%, the weight ratio of tetradecanoic acid, deionized water, sodium hydroxide aqueous solution, and the erbium chloride solution obtained in step (1) is 1:10:12:3, the stirring speed is 400 rpm, and the drying temperature is 75°C; in step (3), the volume fraction of ethanol aqueous solution is 75%, the weight ratio of the modifier obtained in step (2), ethanol aqueous solution, and aluminum silicate is 0.3:50:40, the stirring speed is 200 rpm, and the drying temperature is 75°C.

[0015] Furthermore, the lubricant of the present invention is polyethylene wax.

[0016] Another technical problem to be solved by the present invention is to provide a method for preparing the sizing agent for electronic-grade glass fiber cloth.

[0017] In order to solve the above technical problems, the technical solution is:

[0018] A method for preparing a sizing agent for electronic-grade glass fiber cloth comprises the following steps:

[0019] S1 weighed the raw materials in parts by weight, the film-forming agent, emulsifier was added to 1 / 4 weight of deionized water, stirred at 85-95 ℃ for 12-18 hours to obtain a mixed slurry;

[0020] S2. The guar gum, additives, reinforcing agents, lubricants were added to the remaining deionized water and stirred for 50-60 minutes to obtain a mixture;

[0021] S3. The mixed slurry obtained in step S1 and the mixed solution obtained in step S2 are mixed and stirred for 30-40 minutes to obtain a sizing agent for electronic-grade glass fiber cloth.

[0022] Furthermore, in steps S1, S2, and S3 of the present invention, the stirring speed is 200 rpm.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) The film-forming agent used in the present invention is composed of carboxymethyl starch and polyvinyl alcohol, which has good film-forming properties. The size film formed has good strength and toughness, and the waste liquid generated during desizing has good biodegradability.

[0025] (2) Aluminum silicate is a reinforcing agent with good mechanical properties and wear resistance. However, there are polar functional groups such as hydroxyl groups on its surface, which leads to its poor dispersibility in the sizing agent system. In this regard, the present invention first reacts erbium chloride with concentrated hydrochloric acid to obtain an erbium chloride solution, then conducts a coordination reaction between tetradecanoic acid and the erbium chloride solution to obtain a modifier, and then modifies the aluminum silicate with the modifier to obtain a reinforcing agent. The modifier has a strong complexing ability and can effectively eliminate polar functional groups such as hydroxyl groups on the surface of aluminum silicate, thereby reducing the polarity of the aluminum silicate surface and improving the dispersibility of aluminum silicate in the sizing agent system, thereby improving the mechanical properties and wear resistance of the electronic-grade glass fiber cloth after sizing.

[0026] (3) The present invention also uses methyl glucose polyoxypropylene ether distearate as an auxiliary agent, which can improve the dispersion and sizing effect of the sizing agent, thereby reducing the hairiness of the electronic-grade glass fiber cloth after sizing, and further improving the mechanical properties of the electronic-grade glass fiber cloth after sizing. DETAILED DESCRIPTION

[0027] The present invention will be described in detail below with reference to specific embodiments. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention but are not intended to limit the present invention.

[0028] Example 1

[0029] A sizing agent for electronic-grade glass fiber cloth is prepared from the following raw materials in parts by weight: 5 parts film-forming agent, 0.8 parts guar gum, 0.8 parts emulsifier, 1.4 parts auxiliary agent, 1.8 parts reinforcing agent, 2.5 parts lubricant, and 84 parts deionized water. The film-forming agent is composed of carboxymethyl starch and polyvinyl alcohol 17-99 in a weight ratio of 2:1, the emulsifier is dodecylphenol polyoxyethylene ether, the auxiliary agent is methyl glucose polyoxypropylene ether distearate, and the lubricant is polyethylene wax. The reinforcing agent is prepared by the following steps:

[0030] (1) Add erbium oxide to deionized water, heat to 45° C., start stirring, and add 38% concentrated hydrochloric acid. The weight ratio of erbium oxide, deionized water, and concentrated hydrochloric acid is 1:10:3. Stir at 200 rpm for 30 minutes to obtain an erbium chloride solution.

[0031] (2) dissolving tetradecanoic acid in deionized water, stirring at 400 rpm for 10 minutes, adding a sodium hydroxide aqueous solution having a mass concentration of 0.5%, heating to 90° C. and continuing stirring for 20 minutes, adjusting the pH value to 7, and adding the erbium chloride solution obtained in step (1), wherein the weight ratio of tetradecanoic acid, deionized water, sodium hydroxide aqueous solution, and erbium chloride solution obtained in step (1) is 1:10:12:3, continuing stirring at 90° C. for 2 hours, and then standing to separate into an aqueous phase and an oil phase, discarding the aqueous phase, washing the oil phase with deionized water three times, and then filtering to obtain a filter cake, and placing the filter cake in an oven at 75° C. to dry to a constant weight to obtain a modifier;

[0032] (3) The modifier obtained in step (2) is added to an ethanol aqueous solution at a volume fraction of 75%, and stirred at a speed of 200 rpm for 10 minutes to obtain a modifier solution. Aluminum silicate is added to the modifier solution and stirred for 12 hours to obtain a reaction solution. The weight ratio of the modifier obtained in step (2), the ethanol aqueous solution, and the aluminum silicate is 0.3:50:40. The reaction solution is filtered to obtain a filter cake. The filter cake is washed three times with deionized water and anhydrous ethanol respectively, and then placed in an oven at 75° C. and dried to constant weight to obtain a reinforcing agent.

[0033] The preparation method of Example 1 comprises the following steps:

[0034] S1 weighed the raw materials in parts by weight, the film-forming agent, emulsifier was added to 1 / 4 weight of deionized water, 200 rpm speed, 90 ℃ stirring for 15 hours to obtain a mixed slurry;

[0035] S2. The guar gum, additives, reinforcing agents, and lubricants were added to the remaining deionized water and stirred at 200 rpm for 55 minutes to obtain a mixture;

[0036] S3. The mixed slurry obtained in step S1 and the mixed solution obtained in step S2 are mixed, and stirred at 200 rpm for 35 minutes to obtain a sizing agent for electronic-grade glass fiber cloth.

[0037] Example 2

[0038] A sizing agent for electronic-grade glass fiber cloth is prepared from the following raw materials in parts by weight: 6 parts film-forming agent, 1 part guar gum, 0.9 parts emulsifier, 1.5 parts auxiliary agent, 1.6 parts reinforcing agent, 2 parts lubricant, and 85 parts deionized water. The film-forming agent is composed of carboxymethyl starch and polyvinyl alcohol 17-99 in a weight ratio of 2:1, the emulsifier is dodecylphenol polyoxyethylene ether, the auxiliary agent is methyl glucose polyoxypropylene ether distearate, and the lubricant is polyethylene wax. The preparation steps of the reinforcing agent are the same as those in Example 1.

[0039] The preparation method of Example 2 comprises the following steps:

[0040] S1 weighed the raw materials in parts by weight, the film-forming agent, emulsifier was added to 1 / 4 weight of deionized water, 200 rpm speed, 95 ℃ stirring for 12 hours to obtain a mixed slurry;

[0041] S2. The guar gum, additives, reinforcing agents, and lubricants were added to the remaining deionized water and stirred at 200 rpm for 50 minutes to obtain a mixture;

[0042] S3. The mixed slurry obtained in step S1 and the mixed solution obtained in step S2 are mixed, and stirred at 200 rpm for 30 minutes to obtain a sizing agent for electronic-grade glass fiber cloth.

[0043] Example 3

[0044] A sizing agent for electronic-grade glass fiber cloth is prepared from the following raw materials in parts by weight: 4 parts film-forming agent, 0.7 parts guar gum, 0.7 parts emulsifier, 1.2 parts auxiliary agent, 2 parts reinforcing agent, 3 parts lubricant, and 83 parts deionized water. The film-forming agent is composed of carboxymethyl starch and polyvinyl alcohol 17-99 in a weight ratio of 2:1, the emulsifier is dodecylphenol polyoxyethylene ether, the auxiliary agent is methyl glucose polyoxypropylene ether distearate, and the lubricant is polyethylene wax. The preparation steps of the reinforcing agent are the same as those in Example 1.

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

[0046] S1 weighed the raw materials in parts by weight, the film-forming agent, emulsifier was added to 1 / 4 weight of deionized water, 200 rpm speed, 85 ℃ stirring for 18 hours to obtain a mixed slurry;

[0047] S2. The guar gum, additives, reinforcing agents, and lubricants were added to the remaining deionized water and stirred at 200 rpm for 60 minutes to obtain a mixture;

[0048] S3. The mixed slurry obtained in step S1 and the mixed solution obtained in step S2 are mixed, and stirred at 200 rpm for 40 minutes to obtain a sizing agent for electronic-grade glass fiber cloth.

[0049] Example 4

[0050] A sizing agent for electronic-grade glass fiber cloth is prepared from the following raw materials in parts by weight: 3 parts film-forming agent, 0.5 parts guar gum, 0.6 parts emulsifier, 1 part auxiliary agent, 1.5 parts reinforcing agent, 2.8 parts lubricant, and 82 parts deionized water. The film-forming agent is composed of carboxymethyl starch and polyvinyl alcohol 17-99 in a weight ratio of 2:1, the emulsifier is dodecylphenol polyoxyethylene ether, the auxiliary agent is methyl glucose polyoxypropylene ether distearate, and the lubricant is polyethylene wax. The preparation steps of the reinforcing agent are the same as those in Example 1.

[0051] The preparation method of Example 4 comprises the following steps:

[0052] S1 weighed the raw materials in parts by weight, the film-forming agent, emulsifier was added to 1 / 4 weight of deionized water, 200 rpm speed, 92 ℃ stirring for 16 hours to obtain a mixed slurry;

[0053] S2. The guar gum, additives, reinforcing agents, and lubricants were added to the remaining deionized water and stirred at 200 rpm for 56 minutes to obtain a mixture;

[0054] S3. The mixed slurry obtained in step S1 and the mixed solution obtained in step S2 are mixed, and stirred at 200 rpm for 32 minutes to obtain a sizing agent for electronic-grade glass fiber cloth.

[0055] Comparative Example 1

[0056] The difference from Example 1 is that the raw materials do not include the auxiliary agent - methyl glucose polyoxypropylene ether distearate.

[0057] Comparative Example 2

[0058] The difference from Example 1 is that the reinforcing agent in the raw materials is replaced by aluminum silicate, and the preparation step of the reinforcing agent is omitted.

[0059] Experimental Example 1: Mechanical Properties Test

[0060] The sizing agents prepared in Examples 1-4 and Comparative Examples 1-2 were added to a sizing apparatus to sizing electronic-grade glass fiber yarns. After drying at 110°C, electronic-grade glass fibers with a sizing film formed on their surfaces were obtained. These electronic-grade glass fibers were then woven into electronic-grade glass fiber cloths. The breaking strength of each electronic-grade glass fiber cloth was tested using an electronic tensile testing machine in accordance with JC / T996-2006. A higher breaking strength indicates better mechanical properties. The test results are shown in Table 1.

[0061]

[0062]

[0063] Table 1

[0064] As can be seen from Table 1, the breaking strengths of Examples 1-4 of the present invention are all relatively high, indicating that the sizing agent prepared by the present invention can effectively improve the mechanical properties of electronic-grade glass fiber cloth. Comparative Examples 1-2 use some different raw materials and preparation steps from Example 1. Compared with Example 1, the breaking strength of Comparative Example 1 is reduced, indicating that the auxiliary agent used in the present invention, methyl glucose polyoxypropylene ether distearate, can effectively improve the mechanical properties of electronic-grade glass fiber cloth. Compared with Example 1, the breaking strength of Comparative Example 2 is also reduced, indicating that the reinforcing agent prepared by the present invention has a better effect on improving the mechanical properties of electronic-grade glass fiber cloth than unmodified aluminum silicate.

[0065] Experimental Example 2: Wear resistance test

[0066] The abrasion resistance of the electronic-grade glass fiber cloths (Examples 1-4 and Comparative Example 2) prepared in Experimental Example 1 was tested according to ASTM D 3885-2004. A higher abrasion resistance indicates better abrasion resistance. The test results are shown in Table 2:

[0067] Wear times (times) Example 1 340 Example 2 320 Example 3 355 Example 4 310 Comparative Example 2 290

[0068] Table 2

[0069] As can be seen from Table 2, Examples 1-4 of the present invention all achieved high abrasion resistance times, indicating that the sizing agent prepared by the present invention can effectively improve the wear resistance of electronic-grade glass fiber cloth. Comparative Example 2 uses some different raw materials and preparation steps from Example 1. Compared with Example 1, the abrasion resistance times of Comparative Example 2 are significantly reduced, indicating that the reinforcing agent prepared by the present invention is more effective in improving the wear resistance of electronic-grade glass fiber cloth than unmodified aluminum silicate.

[0070] Experimental Example 3: Hairiness Test

[0071] The hairiness of the electronic-grade glass fiber cloths (Examples 1-4, Comparative Example 1) prepared in Experimental Example 1 was tested with reference to FZ / T01086-2000. The test results are shown in Table 3:

[0072] Hairiness (mg / 500m) Example 1 2.9 Example 2 3.3 Example 3 3.1 Example 4 3.6 Comparative Example 1 6.5

[0073] Table 3

[0074] As can be seen from Table 3, the hairiness of Examples 1-4 of the present invention is relatively low, indicating that the sizing agent prepared by the present invention can effectively reduce the hairiness of electronic-grade glass fiber cloth. Comparative Example 1 uses some different raw materials from Example 1, and the hairiness of Comparative Example 1 is increased compared to Example 1, indicating that the auxiliary agent used in the present invention, methyl glucose polyoxypropylene ether distearate, can effectively reduce the hairiness of electronic-grade glass fiber cloth.

[0075] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A sizing agent for electronic grade glass fiber cloth, characterized in that: The invention is prepared from the following raw materials in parts by weight: 3-6 parts of film-forming agent, 0.5-1 part of guar gum, 0.6-0.9 part of emulsifier, 1-1.5 parts of auxiliary agent, 1.5-2 parts of reinforcing agent, 2-3 parts of lubricant, and 82-85 parts of deionized water; the auxiliary agent is methyl glucose polyoxypropylene ether distearate; The reinforcing agent is prepared by the following steps: (1) Add erbium oxide to deionized water, heat to 45°C, start stirring, add concentrated hydrochloric acid, and stir for 30 minutes to obtain an erbium chloride solution; (2) Tetradecanoic acid was dissolved in deionized water, stirred for 10 minutes, and then a sodium hydroxide aqueous solution was added. The mixture was heated to 90°C and stirred for 20 minutes. The pH value was adjusted to 7, and then the erbium chloride solution obtained in step (1) was added. The mixture was stirred at 90°C for 2 hours, and then allowed to stand and separate into an aqueous phase and an oil phase. The aqueous phase was discarded, and the oil phase was washed with deionized water three times and then filtered to obtain a filter cake. The filter cake was placed in an oven and dried to a constant weight to obtain a modifier. (3) The modifier obtained in step (2) was added to an ethanol aqueous solution, and the mixture was stirred for 10 minutes to obtain a modifier solution. Aluminum silicate was added to the modifier solution and the mixture was stirred for 12 hours to obtain a reaction solution. The reaction solution was filtered to obtain a filter cake. The filter cake was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in an oven to a constant weight to obtain a reinforcing agent.

2. The sizing agent for electronic-grade glass fiber cloth according to claim 1, wherein: The film-forming agent consists of carboxymethyl starch and polyvinyl alcohol 17-99 in a weight ratio of 2:

1.

3. The sizing agent for electronic-grade glass fiber cloth according to claim 1, wherein: The emulsifier is dodecylphenol polyoxyethylene ether.

4. The sizing agent for electronic-grade glass fiber cloth according to claim 1, wherein: In the step (1), the mass concentration of concentrated hydrochloric acid is 38%, the weight ratio of erbium oxide, deionized water, and concentrated hydrochloric acid is 1:10:3, and the stirring speed is 200 rpm; in the step (2), the mass concentration of the sodium hydroxide aqueous solution is 0.5%, the weight ratio of tetradecanoic acid, deionized water, the sodium hydroxide aqueous solution, and the erbium chloride solution obtained in the step (1) is 1:10:12:3, the stirring speed is 400 rpm, and the drying temperature is 75°C; in the step (3), the volume fraction of the ethanol aqueous solution is 75%, the weight ratio of the modifier obtained in the step (2), the ethanol aqueous solution, and the aluminum silicate is 0.3:50:40, the stirring speed is 200 rpm, and the drying temperature is 75°C.

5. The sizing agent for electronic-grade glass fiber cloth according to claim 1, characterized in that: The lubricant is polyethylene wax.

6. The method for preparing a sizing agent for electronic-grade glass fiber cloth according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1 weighed the raw materials in parts by weight, the film-forming agent, emulsifier was added to 1 / 4 weight of deionized water, stirred at 85-95 ℃ for 12-18 hours to obtain a mixed slurry; S2. The guar gum, additives, reinforcing agents, lubricants were added to the remaining deionized water and stirred for 50-60 minutes to obtain a mixture; S3. The mixed slurry obtained in step S1 and the mixed solution obtained in step S2 are mixed and stirred for 30-40 minutes to obtain a sizing agent for electronic-grade glass fiber cloth.

7. The method for preparing a sizing agent for electronic-grade glass fiber cloth according to claim 6, wherein: In steps S1, S2, and S3, the stirring speed is 200 rpm.

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