CN101736593B - Preparation method of water-base epoxy resin sizing agent for carbon fiber - Google Patents

Abstract

The invention discloses a preparation method of a water-based epoxy resin sizing agent for carbon fibers, which relates to a preparation method of the sizing agent. The invention solves the problems of high cost of the existing foreign emulsion-type sizing agent and poor performance of the domestically researched emulsion-type sizing agent. Method: 1. Prepare water-based epoxy resin; 2. Prepare water-soluble epoxy resin curing agent; 3. Dilute the water-based epoxy resin with deionized water and then disperse to obtain water-based epoxy resin emulsion; 4. Water-based epoxy resin Mix the emulsion with a water-soluble epoxy resin curing agent to obtain a water-based epoxy resin emulsion system; 5. Mix the water-based epoxy resin emulsion system and additives to obtain a water-based epoxy resin sizing agent for carbon fibers. The water-based epoxy resin sizing agent for carbon fibers of the present invention has good performance, good reinforcing effect on carbon fibers, good bundling, smoothness, and flexibility, and can simultaneously satisfy the overall looseness of filaments between fibers, fiber opening, The performance index of crosslinking degree between single fibers, and the cost is low.

Description

A kind of preparation method of water-based epoxy resin sizing agent for carbon fiber

technical field

The invention relates to a preparation method of a sizing agent.

Background technique

Carbon fiber is a brittle material. In the process of production and processing, it is easy to produce wool and monofilament breakage through mechanical friction, which reduces the strength of carbon fiber. Moreover, due to the existence of wool, the matrix resin cannot fully wet the carbon fiber, making it It is easy to produce pores in the prepared composite material, which will affect the mechanical properties of the composite material, and the wool will also affect the working environment. Therefore, it is necessary to sizing the carbon fiber. The function of sizing is to form a protective film on the surface of the carbon fiber, which not only protects the surface of the carbon fiber during subsequent processing, reduces the breakage of wool and single filaments, but also makes the carbon fiber easy to be bundled. It acts as a transition layer to improve the compatibility between carbon fiber and matrix resin, thereby improving the interfacial bonding of composite materials.

At present, carbon fiber sizing agents can be divided into two types, one is solution type, which dissolves organic resins such as polyvinyl alcohol, vinyl acetate polymers, acrylic polymers, polyurethanes, epoxy resins, etc. in organic solvents such as acetone But the solution type sizing agent needs a lot of flammable organic solvents, which will bring problems in economy, safety and sanitation. The other is an emulsion type, which is based on a resin, mixed with a quantitative emulsifier and sometimes contains a small amount of crosslinking agent, depending on the nature of the resin, and an emulsion made of additives to improve interface adhesion. Generally, it is not easy to leave resin on the guide roller, and there is no solvent to pollute the environment, and because the emulsion contains surfactants, the wettability of the fiber surface is improved, and at the same time, it can be improved through auxiliary agents and coupling agents. Therefore, emulsion-type sizing agents are widely used abroad, but the cost of emulsion-type sizing agents is high, which limits their popularization and application; at present, the performance of emulsion-type sizing agents researched in China is not very ideal, and it cannot ensure that carbon fibers have good clustering and smoothness at the same time , softness, flexibility, etc., and cannot simultaneously meet performance indicators such as the overall looseness of the filaments between fibers, fiber opening, and cross-linking degree between single fibers, and cannot meet the current production needs and market needs.

Contents of the invention

In order to solve the problems that the cost of the existing foreign emulsion-type sizing agent is high; the performance of the domestically-researched emulsion-type sizing agent is not good, and the reinforcing effect on carbon fiber is poor, the present invention provides a preparation method of a carbon fiber water-based epoxy resin sizing agent .

The preparation method of carbon fiber water-based epoxy resin sizing agent is realized by the following steps: 1. Add epoxy resin and water-based epoxy emulsifier in a mass ratio of 80:20 in a water bath at 70°C, and then place it in a high-shear dispersing emulsifier Stir at a speed of 1500-16000r/min, and add deionized water dropwise until the phase transfer occurs in the mixed system, then add deionized water dropwise after 20-90 minutes until the solid content of the mixed system is 40%-50%, continue Stir for 30 minutes to obtain water-based epoxy resin HIT-WE; 2. Add epoxy resin curing agent and water-based epoxy emulsifier in a water bath at 70°C in a mass ratio of 80:20, and then place it in a high-shear dispersing emulsifier. Stir at a speed of 1500-8000r/min and add deionized water dropwise, and then add deionized water dropwise after 3-5 hours until the solid content of the mixed system is 40%-50%, to obtain a water-soluble epoxy resin curing agent HIT- GY; 3. Dilute the water-based epoxy resin HIT-WE with deionized water to a solid content of 0.5% to 5%, and then disperse to a particle size of 100-500nm to obtain a water-based epoxy resin emulsion HIT-Y; 4. Press Mass ratio 100: 0.01～0.25 Mix water-based epoxy resin emulsion HIT-Y with water-soluble epoxy resin curing agent HIT-GY to obtain water-based epoxy resin emulsion system HIT-S; % of the water-based epoxy resin emulsion system HIT-S and 2% to 10% of additives are mixed to obtain a water-based epoxy resin sizing agent for carbon fibers; wherein the epoxy resin curing agent in step 2 is triethylenetetramine, p-phenylene Diamine, aliphatic amine or aromatic diamine; the dispersion in step 3 is to use a high-shear dispersing emulsifier to disperse at a speed of 3000-8000r/min or ultrasonic dispersion for 10-30min; the auxiliary agent in step 5 is fatty acid SR- GWS and aliphatic amide SR-508.

The carbon fiber water-based epoxy resin sizing agent of the present invention has good compatibility with the commonly used resin matrix, can simultaneously achieve the purpose of protecting the carbon fiber surface and enhancing the bonding strength between the carbon fiber and the resin matrix, and can give full play to the excellent properties of the carbon fiber Performance, can give carbon fiber sufficient bundle, excellent mechanical properties and low saturated water absorption (<0.6%). The carbon fiber water-based epoxy resin sizing agent of the present invention has good permeability and can penetrate into the inside of the fiber for bonding; good water solubility and easy gluing; good bonding strength and endows carbon fiber with good processing High performance, to withstand tension and friction; no glue falling, no glue, wide adaptability to temperature and humidity. The carbon fiber water-based epoxy resin sizing agent of the present invention has good performance, has a good reinforcing effect on carbon fibers, and can simultaneously ensure that carbon fibers have better bundling properties, smoothness, softness, and flexibility, and can simultaneously meet the overall requirements of the filaments between fibers. The degree of looseness, the degree of fiber opening, and the degree of crosslinking between individual fibers are performance indicators. The preparation method of the invention is simple, the cost is low, and the needs of the current production and the market are met.

Description of drawings

Fig. 1 is the scanning electron micrograph of the cross-section of the composite material prepared from the carbon fiber after the carbon fiber is sized with the water-based epoxy resin sizing agent in the eleventh embodiment; Fig. 2 is the sizing after the existing sizing agent is used in the eleventh embodiment Scanning electron micrograph of the cross-section of carbon fibers prepared into composite materials.

Detailed ways

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific embodiment one: the preparation method of carbon fiber water-based epoxy resin sizing agent in this embodiment is realized by the following steps: one, add epoxy resin and water-based epoxy emulsifier by mass ratio 80:20 in the water bath of 70 ℃, then Place in a high-shear dispersing emulsifier, stir at a speed of 1500-16000r/min, and add deionized water dropwise until the phase transfer occurs in the mixed system, and then add deionized water dropwise to the solid content of the mixed system after 20-90 minutes 40% to 50%, continue to stir for 30 minutes to obtain water-based epoxy resin HIT-WE; 2. Add epoxy resin curing agent and water-based epoxy emulsifier in a water bath at 70°C in a mass ratio of 80:20, and then place In the high-shear dispersing emulsifier, stir at a speed of 1500-8000r/min and add deionized water dropwise, and then add deionized water dropwise after 3-5 hours until the solid content of the mixed system is 40%-50%. 3. Dilute the water-based epoxy resin HIT-WE with deionized water to a solid content of 0.5% to 5%, and then disperse to a particle size of 100-500nm to obtain a water-based epoxy resin Emulsion HIT-Y; 4. Mix the water-based epoxy resin emulsion HITY with the water-soluble epoxy resin curing agent HIT-GY according to the mass ratio of 100:0.01~0.25 to obtain the water-based epoxy resin emulsion system HIT-S; 5. According to the quality Percentage Mix 90%~98% of water-based epoxy resin emulsion system HIT-S and 2%~10% of additives to get water-based epoxy resin sizing agent for carbon fiber; the epoxy resin curing agent in step 2 is three Ethylenetetramine, p-phenylenediamine, aliphatic amine or aromatic diamine; the dispersion in step three is to use a high-shear dispersing emulsifier to disperse at a speed of 3000-8000r/min or ultrasonic dispersion for 10-30min; in step five The additives are fatty acid SR-GWS and fatty acid amide SR-508.

The model of the high-shear dispersing and emulsifying machine in Step 1 of this embodiment is FA25, which is produced by Shanghai Fluke Electromechanical Equipment Co., Ltd.

In step 1 of this embodiment, the phase transfer occurs in the mixed system, that is, the viscosity of the system drops instantaneously, and the electrical conductivity begins to drop suddenly.

In the third step of this embodiment, the water-based epoxy resin emulsion HIT-Y has a particle size of 100-500nm, the particle size can be controlled, the particle distribution is narrow (100-300nm), good stability (>6 months), and temperature resistance Preferably, the saturated water absorption rate is low (<0.1%), and it is environmentally friendly and pollution-free.

Both the fatty acid SR-GWS and the fatty acid amide SR-508 in Step 5 of this embodiment are purchased directly.

Specific embodiment two: the difference between this embodiment and specific embodiment one is the preparation of water-based epoxy emulsifier in step one: the 250ml four-necked bottle equipped with agitator, reflux condenser and thermometer is placed in 80 ℃ water bath , then add bisphenol A epoxy resin and polyethylene glycol in a molar ratio of 1:1, and stir at a rate of 200 to 500r/min until molten state; heat up to 100°C, add bisphenol A epoxy resin and triphenylphosphine with 0.15% of the total mass of polyethylene glycol, and stirred at a rate of 200-500r/min for 6h, then pour the product into a watch glass to obtain a water-based epoxy emulsifier; put it into a desiccator for preservation . Other steps and parameters are the same as those in Embodiment 1.

Specific embodiment 3: The difference between this embodiment and specific embodiment 1 is that in step 1, stirring is performed at a rotational speed of 2000-10000 r/min. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 4: This embodiment is different from Embodiment 1 in that step 1 stirs at a speed of 8000 r/min. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 5: This embodiment is different from Embodiment 4 in that deionized water is added dropwise after 60 minutes in step 1 until the solid content of the mixed system is 50%. Other steps and parameters are the same as those in Embodiment 4.

Specific embodiment six: the difference between this embodiment and specific embodiment five is that in step three, water-based epoxy resin HIT-WE is diluted to a solid content of 3% to 4% with deionized water, and then dispersed to a particle size of 200 to 4%. 400nm. Other steps and parameters are the same as those in Embodiment 5.

Embodiment 7: The difference between this embodiment and Embodiment 5 is that in step 3, the water-based epoxy resin HIT-WE is diluted with deionized water to a solid content of 3.5%, and then dispersed to a particle size of 300nm. Other steps and parameters are the same as those in Embodiment 5.

Embodiment 8: The difference between this embodiment and Embodiment 6 or 7 is that the water-based epoxy resin emulsion HIT-Y and the water-soluble epoxy resin curing agent HIT-GY are mixed according to the mass ratio of 100:0.011 in Step 4 in Step 4. Mix to obtain the water-based epoxy resin emulsion system HIT-S. Other steps and parameters are the same as those in Embodiment 6 or 7.

Embodiment 9: The difference between this embodiment and Embodiment 8 is that in step 5, 92% to 96% of the water-based epoxy resin emulsion system HIT-S and 4% to 8% of additives are mixed according to mass percentage. Other steps and parameters are the same as those in Embodiment 8.

Embodiment 10: This embodiment is different from Embodiment 8 in that in step 5, 98% of the water-based epoxy resin emulsion system HIT-S and 2% of additives are mixed by mass percentage. Other steps and parameters are the same as those in Embodiment 8.

Embodiment Eleven: The preparation method of carbon fiber water-based epoxy resin sizing agent in this embodiment is realized according to the following steps: 1. Add epoxy resin and water-based epoxy emulsifier at a mass ratio of 80:20 in a water bath at 70°C, Then put it in a high-shear dispersing emulsifier, stir at a speed of 8000r/min, and add deionized water dropwise until the phase transfer occurs in the mixed system, and then add deionized water dropwise after 60 minutes until the solid content of the mixed system is 50%. , and continue to stir for 30 minutes to obtain water-based epoxy resin HIT-WE; 2. Add epoxy resin curing agent and water-based epoxy emulsifier in a mass ratio of 80:20 in a water bath at 70 ° C, and then place it in a high-shear dispersing emulsifier In the process, stir at a speed of 4000r/min and add deionized water dropwise, and then add deionized water dropwise after 4 hours until the solid content of the mixed system is 50%, to obtain the water-soluble epoxy resin curing agent HIT-GY; 3. Use Dilute the water-based epoxy resin HIT-WE with deionized water to a solid content of 3%, and then disperse it to a particle size of 200nm to obtain a water-based epoxy resin emulsion HIT-Y; Emulsion HIT-Y mixes with water-soluble epoxy resin curing agent HIT-GY to obtain water-based epoxy resin emulsion system HIT-S; five, mix 98% of water-based epoxy resin emulsion system HIT-S and 2% of Auxiliaries are mixed to obtain a water-based epoxy resin sizing agent for carbon fibers; the epoxy resin curing agent in step two is triethylenetetramine; the dispersion in step three is to use a high-shear dispersing emulsifier to disperse at a speed of 5000r/min ; Auxiliaries in step five are fatty acid SR-GWS and fatty acid amide SR-508.

In this embodiment, the carbon fiber water-based epoxy resin sizing agent is used in the carbon fiber production line to sizing the carbon fiber, and then dried at 120-150° C., and then collected.

The performance and saturated water absorption of the sized carbon fibers were tested, and the results are shown in Table 1. The sizing agent in this embodiment has good performance and can make the carbon fibers have excellent mechanical properties and low saturated water absorption. The tensile strength of carbon fiber before sizing is 3.30, and it is brittle and easy to fold.

Table 1

Tensile strength Gpa Strength cv value % Elongation at break% Elongation at break cv value%  Gel content% Saturated water absorption% 3.36 4.7 2.07 6.21 1.32 0.05

In this embodiment, carbon fibers sizing with water-based epoxy resin sizing agent are used to prepare composite materials. It can be seen from Figure 1 that the ports of the composite materials are very neat and there is no pull-out phenomenon, indicating that the direct bonding force between the fiber and the resin is very good. The compatibility of the two is good. However, for the composite material prepared by using the carbon fiber sized by the existing sizing agent, it can be seen from Figure 2 that the fiber is pulled out at the port of the composite material, and the interface bonding is poor.

In this embodiment, the carbon fiber water-based epoxy resin sizing agent and the 4# sizing agent produced in Japan are sizing a carbon fiber at the same time, and the interlayer shear force is tested, which are 87.06331 and 85.58375 respectively. It can be seen that the sizing in this embodiment is used The agent performance is better than the 4# sizing agent produced in Japan.

In this embodiment, the water-based epoxy resin sizing agent for carbon fiber and the 4# sizing agent produced in Japan, after sizing a kind of carbon fiber at the same time, analyze the temperature resistance of the sizing agent. The results are shown in Table 2. In this embodiment, the carbon fiber is used The water-based epoxy resin sizing agent has good heat resistance, which can prevent the structure and performance of carbon fiber from being damaged at high temperature.

Table 2

sample  Decomposition temperature/°C  Maximum decomposition temperature/℃ Sizing amount/% Carbon fiber water-based epoxy resin sizing agent 197 346 1.3 Japan 4# sizing agent 178 319 0.9

Embodiment 12: The preparation method of carbon fiber water-based epoxy resin sizing agent in this embodiment is realized according to the following steps: 1. Add epoxy resin and water-based epoxy emulsifier at a mass ratio of 80:20 in a water bath at 70°C, Then put it in a high-shear dispersing emulsifier, stir at a speed of 10000r/min, and add deionized water dropwise until the phase transfer occurs in the mixed system, and then add deionized water dropwise after 50 minutes until the solid content of the mixed system is 40%. , and continue to stir for 30 minutes to obtain water-based epoxy resin HIT-WE; 2. Add epoxy resin curing agent and water-based epoxy emulsifier at a mass ratio of 80:20 in a water bath at 70 ° C, and then place it in a high-shear dispersing emulsifier In the process, stir at a speed of 6000r/min and add deionized water dropwise, and then add deionized water dropwise after 5 hours until the solid content of the mixed system is 40%, to obtain the water-soluble epoxy resin curing agent HIT-GY; 3. Use Dilute the water-based epoxy resin HIT-WE with deionized water to a solid content of 4%, and then disperse it to a particle size of 100nm to obtain a water-based epoxy resin emulsion HIT-Y; Emulsion HIT-Y mixes with water-soluble epoxy resin curing agent HIT-GY to obtain water-based epoxy resin emulsion system HIT-S; five, mix 92% water-based epoxy resin emulsion system HIT-S and 8% of Additives are mixed to obtain a water-based epoxy resin sizing agent for carbon fiber; the epoxy resin curing agent in step 2 is p-phenylenediamine; the dispersion in step 3 is ultrasonic dispersion for 30 minutes; the auxiliary agent in step 5 is fatty acid SR-GWS and aliphatic amide SR-508.

In this embodiment, the carbon fiber water-based epoxy resin sizing agent is used in the carbon fiber production line to sizing the carbon fiber, and then dried at 120-150° C., and then collected.

The performance and saturated water absorption of the sized carbon fibers were tested, and the results are shown in Table 3. The sizing agent in this embodiment has good performance and can make the carbon fibers have excellent mechanical properties and low saturated water absorption.

table 3

Tensile strength Gpa Strength cv value % Elongation at break% Elongation at break cv value%  Gel content% Saturated water absorption% 3.45 4.71 1.98 5.16 1.28 0.05

Specific Embodiment Thirteen: The preparation method of carbon fiber water-based epoxy resin sizing agent in this embodiment is realized by the following steps: 1. Add epoxy resin and water-based epoxy emulsifier at a mass ratio of 80:20 in a water bath at 70°C, Then put it in a high-shear dispersing emulsifier, stir at a speed of 12000r/min, and add deionized water dropwise until the phase transfer occurs in the mixed system, and then add deionized water dropwise after 80 minutes until the solid content of the mixed system is 45%. , and continue to stir for 30 minutes to obtain water-based epoxy resin HIT-WE; 2. Add epoxy resin curing agent and water-based epoxy emulsifier at a mass ratio of 80:20 in a water bath at 70 ° C, and then place it in a high-shear dispersing emulsifier In the process, stir at a speed of 7000r/min and add deionized water dropwise, and then add deionized water dropwise after 3 hours until the solid content of the mixed system is 45%, to obtain the water-soluble epoxy resin curing agent HIT-GY; 3. Use Dilute the water-based epoxy resin HIT-WE with deionized water to a solid content of 2%, and then disperse it to a particle size of 300nm to obtain a water-based epoxy resin emulsion HIT-Y; Emulsion HIT-Y mixes with water-soluble epoxy resin curing agent HIT-GY to obtain water-based epoxy resin emulsion system HIT-S; five, mix 97% of water-based epoxy resin emulsion system HIT-S and 3% of Auxiliaries are mixed to obtain a water-based epoxy resin sizing agent for carbon fiber; wherein the epoxy resin curing agent is an aliphatic amine in step two; the dispersion in step three is to adopt ultrasonic dispersion for 25min; the auxiliaries in step five are fatty acid SR-GWS and Aliphatic amide SR-508.

In this embodiment, the carbon fiber water-based epoxy resin sizing agent is used in the carbon fiber production line to sizing the carbon fiber, and then dried at 120-150° C., and then collected.

The performance and saturated water absorption of the sized carbon fibers were tested, and the results are shown in Table 4. The sizing agent in this embodiment has good performance and can make the carbon fibers have excellent mechanical properties and low saturated water absorption.

Table 4

Tensile strength Gpa Strength cv value% Elongation at break% Elongation at break cv value%  Gel content% Saturated water absorption% 3.35 5.72 1.83 7.18 1.40 0.06

Claims (10)

1. A preparation method of water-based epoxy resin sizing agent for carbon fiber, characterized in that the preparation method of water-based epoxy resin sizing agent for carbon fiber is realized in the following steps: one, add by mass ratio 80:20 in the water bath of 70 ℃ Epoxy resin and water-based epoxy emulsifier are then placed in a high-shear dispersing emulsifier, stirred at a speed of 1500-16000r/min, and deionized water is added dropwise until the phase transfer occurs in the mixed system. Add deionized water dropwise until the solid content of the mixed system is 40% to 50%, and continue to stir for 30 minutes to obtain water-based epoxy resin HIT-WE; 2. Add epoxy resin in a water bath at 70°C in a mass ratio of 80:20 to cure agent and water-based epoxy emulsifier, then put it in a high-shear dispersing emulsifier, stir at a speed of 1500-8000r/min and add deionized water dropwise, and then add deionized water dropwise to the mixing system after 3-5 hours The solid content is 40% to 50%, and the water-soluble epoxy resin curing agent HIT-GY is obtained; 3. Dilute the water-based epoxy resin HIT-WE with deionized water to a solid content of 0.5% to 5%, and then disperse to the granular The diameter is 100-500nm to obtain water-based epoxy resin emulsion HIT-Y; 4. Mix water-based epoxy resin emulsion HIT-Y with water-soluble epoxy resin curing agent HIT-GY according to the mass ratio of 100:0.01-0.25 to obtain water-based Epoxy resin emulsion system HIT-S; 5. Mix 90%-98% water-based epoxy resin emulsion system HIT-S and 2%-10% additives according to mass percentage to obtain carbon fiber water-based epoxy resin sizing agent; wherein the epoxy resin curing agent in step two is triethylenetetramine or p-phenylenediamine; the dispersion in step three is to use a high-shear dispersing emulsifier to disperse at a speed of 3000-8000r/min or to use ultrasonic dispersion for 10- 30min; the additives in step five are fatty acid SR-GWS and fatty acid amide SR-508. 2. the preparation method of a kind of water-based epoxy resin sizing agent for carbon fiber according to claim 1 is characterized in that the preparation of water-based epoxy emulsifier in step 1: 250ml of agitator, reflux condenser and thermometer are housed Place the four-necked bottle in an 80°C water bath, then add bisphenol A epoxy resin and polyethylene glycol at a molar ratio of 1:1, and stir at a rate of 200-500r/min until molten; heat up to 100°C , add triphenylphosphine accounting for 0.15% of the total mass of bisphenol A epoxy resin and polyethylene glycol, and stir at a rate of 200-500r/min for 6h, then pour the product into a watch glass to obtain a water-based ring oxygen emulsifier. 3. The method for preparing a water-based epoxy resin sizing agent for carbon fibers according to claim 1, characterized in that in step 1, stirring is performed at a speed of 2000-10000 r/min. 4. The preparation method of a kind of carbon fiber water-based epoxy resin sizing agent according to claim 1, characterized in that in step 1, stirring is carried out at a rotating speed of 8000r/min. 5. The preparation method of a water-based epoxy resin sizing agent for carbon fibers according to claim 4, characterized in that in step 1, deionized water is added dropwise after 60 minutes until the solid content of the mixed system is 50%. 6. The preparation method of a water-based epoxy resin sizing agent for carbon fibers according to claim 5, characterized in that in step 3, the water-based epoxy resin HIT-WE is diluted to a solid content of 3% to 4% with deionized water. %, and then dispersed to a particle size of 200-400nm. 7. the preparation method of a kind of carbon fiber waterborne epoxy resin sizing agent according to claim 5 is characterized in that in step 3 waterborne epoxy resin HIT-WE is diluted to solid content with deionized water and is 3.5%, then Disperse to a particle size of 300nm. 8. The preparation method of a kind of carbon fiber water-based epoxy resin sizing agent according to claim 6 or 7, is characterized in that in step 4, water-based epoxy resin emulsion HIT-Y and water-soluble epoxy resin are mixed by mass ratio 100:0.011 Mix epoxy resin curing agent HIT-GY to get water-based epoxy resin emulsion system HIT-S. 9. The preparation method of a water-based epoxy resin sizing agent for carbon fibers according to claim 8, characterized in that in step 5, 92% to 96% of the water-based epoxy resin emulsion system HIT-S and 4 %～8% additives mixed. 10. the preparation method of a kind of water-based epoxy resin sizing agent for carbon fiber according to claim 8, is characterized in that in step 5, 98% of water-based epoxy resin emulsion system HIT-S and 2% of Auxiliary mix.

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