CN111574070A

CN111574070A - Glass fiber impregnating compound and production method of glass fiber

Info

Publication number: CN111574070A
Application number: CN202010354284.XA
Authority: CN
Inventors: 张国平
Original assignee: Qingyuan Kairongde Glass Fibre Co ltd
Current assignee: Qingyuan Kairongde Electronic Special Materials Co ltd
Priority date: 2020-04-29
Filing date: 2020-04-29
Publication date: 2020-08-25
Anticipated expiration: 2040-04-29
Also published as: CN111574070B

Abstract

The invention discloses a glass fiber impregnating compound and a production method of glass fibers, and belongs to the field of industrial production of glass fibers. The impregnating compound comprises raw materials of epoxy resin emulsion, polyvinyl acetate emulsion, coupling agent, acetic acid, acrylate emulsion, dibutyl phthalate, alkyl trimethylammonium chloride, stearic acid, polyethylene glycol, fatty amide, ammonium chloride, preservative and deionized water. The glass fiber is soaked by the sizing agent with excellent performance, so that the mechanical strength and the corrosion resistance of the glass fiber are improved, and the strand adhesion of the glass fiber is increased by using the sizing agent.

Description

Glass fiber impregnating compound and production method of glass fiber

Technical Field

The invention belongs to the field of industrial production of glass fibers, and particularly relates to a glass fiber impregnating compound and a production method of glass fibers.

Background

The glass fiber is an inorganic non-metallic material with excellent performance and a wide variety of types, has the advantages of good insulativity, high mechanical strength, good heat resistance, good corrosion resistance and the like, and also has the defects of poor wear resistance, brittle property and the like. The preparation process is mainly summarized by the working procedures of high-temperature melting, wire drawing, winding, weaving and the like, the diameter of a single filament can reach several micrometers to twenty-several micrometers, which is equivalent to 1/20-1/5 of a hair, and the glass fiber is generally used as a reinforcing material in an electric insulating material, a heat insulation material and a composite material and is distributed in various fields in national life.

In the production process of glass fiber, wherein in the drawing process, the surface of the glass fiber needs to be coated with a surface treatment agent which is mainly solution or has a multiphase structure of organic solution emulsion, the surface treatment material is also called a sizing agent, the performance of the sizing agent greatly determines the quality of the glass fiber, and the sizing agent can not only enhance the adhesion, the fuzzing resistance and the coating performance of a fiber bundle, smoothen the surface of the fiber, increase the wear resistance and the flexibility, but also be easy to wind and reduce the damage during winding. But also is beneficial to the subsequent processing process of the glass fiber, and can promote the combination of the glass fiber and the reinforced high molecular polymer when being compounded with other materials.

CN102020427A discloses a glass fiber impregnating compound, which mainly comprises epoxy resin emulsion, ammonia water or acetic acid, white oil, gasoline and water. The glass fiber soaked by the glass fiber soaking agent has poor wear resistance, alkali resistance, water resistance and antistatic property, and low product qualification rate.

CN106587659B discloses a glass fiber sizing agent and application thereof, wherein the glass fiber sizing agent mainly comprises a coupling agent, a lubricant, an unsaturated polyester emulsion, a polyvinyl acetate emulsion, an epoxy emulsion, a polyurethane emulsion, a pH value regulator and water. Wherein the coupling agent comprises methacryloxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane, the lubricant is polyimide lubricant, and the pH regulator is acetic acid. The impregnating agents prepared in the examples and comparative examples were applied to the production of glass fibers, and the properties of the glass fibers were tested. The comparison of the data of the comparative examples shows that the average hairiness measured in the examples is 8.56mg/kg, the hairiness of the comparative examples is 14.40mg/kg, the hairiness is reduced by 40.5%, which shows that the sizing agent greatly improves the bundling property of the glass fiber, compared with the comparative examples, the average bending strength of the sample is improved by 23.03%, the average unnotched impact strength is improved by 36.49%, the average tensile strength is improved by 5.97%, and the used raw material film forming agent, coupling agent, lubricant and pH value regulator are combined, so that the prepared glass fiber is uniform in glass fiber distribution in the molding process, good in compatibility of the glass fiber and resin, and excellent in appearance effect and mechanical property.

CN108529900A discloses a preparation method of a glass fiber sizing agent, the raw material used in the preparation method is corn starch, the corn starch is firstly mixed with distilled water, the mixture is heated to be pasted, pullulanase is added for enzymolysis, then cooling and drying are carried out to obtain screened particles, the screened particles are secondly mixed with distilled water, the mixture is heated, phosphate buffer solution is added for stirring, isoamylase is added for enzymolysis, formaldehyde with the mass fraction of 95% is added for extraction after filtration, reduced pressure distillation and freeze drying are carried out to obtain dried substance, the dried substance is then mixed with silica gel, glycerol and water, methanol, sodium hydroxide solution, polyethylene glycol, epoxypropane and epichlorohydrin are sequentially added for stirring, filter residue is obtained, and the filter residue is mixed with a self-made sizing agent auxiliary agent to obtain the glass fiber sizing agent. The performance test of the prepared glass fiber impregnating compound impregnated glass fiber shows that the strength of the glass fiber reinforced plastic in distilled water is 133.6-136.5MPa after 7 days, the interfacial shear strength of the glass fiber is 56.4-58.6MPa, and the performance is improved to a certain extent, but the preparation process is complex, the used raw material components are more, and the large-scale industrial production is not easy to carry out.

In order to research a glass fiber sizing agent with excellent performance, research personnel carry out a great deal of research, and the existing glass fiber sizing agent also has the problems of complicated preparation method, poor film forming property, poor bonding force and the like, so that the glass fiber sizing agent which is simple in production method, has excellent mechanical property, and good alkali resistance and wear resistance to the prepared glass fiber sizing agent for sizing glass fibers is urgently needed to be provided.

Disclosure of Invention

In view of the defects indicated by the background technology, the invention provides a glass fiber impregnating compound and a production method of glass fibers, the prepared glass fiber impregnating compound has good film forming property and good bonding property, and the glass fibers impregnated by the glass fiber impregnating compound have excellent alkali resistance, wear resistance and mechanical property.

In order to achieve the purpose, the invention adopts the following technical scheme:

a glass fiber sizing agent comprises the following raw materials: epoxy resin emulsion, polyvinyl acetate emulsion, coupling agent, acetic acid, acrylate emulsion, dibutyl phthalate, alkyl trimethylammonium chloride, stearic acid, polyethylene glycol, fatty amide, ammonium chloride, preservative and deionized water.

Further, the glass fiber impregnating compound comprises the following raw materials in percentage by weight: 8-12% of epoxy resin emulsion, 12-18% of polyvinyl acetate emulsion, 0.6-2.1% of coupling agent, 0.3-0.9% of acetic acid, 5-10% of acrylate emulsion, 0.1-0.5% of dibutyl phthalate, 0.01-0.05% of alkyl trimethylammonium chloride, 0.2-0.8% of stearic acid, 0.5-2% of polyethylene glycol, 0.1-0.25% of fatty amide, 0.2-0.7% of ammonium chloride, 0.3-0.8% of preservative and the balance of deionized water.

Preferably, the glass fiber sizing agent comprises the following raw materials in percentage by weight: 9-11% of epoxy resin emulsion, 14-16% of polyvinyl acetate emulsion, 0.6-1.8% of coupling agent, 0.4-0.8% of acetic acid, 6-9% of acrylate emulsion, 0.2-0.4% of dibutyl phthalate, 0.02-0.05% of alkyl trimethylammonium chloride, 0.3-0.8% of stearic acid, 0.5-1.5% of polyethylene glycol, 0.15-0.25% of fatty amide, 0.3-0.6% of ammonium chloride, 0.4-0.7% of preservative and the balance of deionized water.

Further, the polyethylene glycol is one or more of polyethylene glycol 4000, polyethylene glycol 6000 and polyethylene glycol 3000, and preferably polyethylene glycol 4000.

Further, the alkyl trimethyl ammonium chloride is one or more of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.

Further, the fatty amide is one or more of N, N-dimethylpropyl erucamide, behenic acid amide and stearic acid amide.

Further, the coupling agent is methacryloxypropyltrimethoxysilane and gamma-chloropropyltrimethoxysilane in a weight ratio of 3-1: 1.

Furthermore, the weight ratio of the epoxy resin emulsion to the polyvinyl acetate emulsion is 1: 1-2.

Further, the weight ratio of the dibutyl phthalate to the alkyl trimethylammonium chloride is 10-35: 1.

Further, the weight ratio of the polyethylene glycol to the fatty amide to the ammonium chloride is 8-15:1: 1-20.

Further, the preservative is one or more of formaldehyde, organic nitrogen sulfide and organic tin compound.

The invention also provides a production method of the glass fiber soaked by the glass fiber soaking agent, which comprises the following steps:

s1, mixing the raw materials of silica sand, kaolin, calcite, fluorite, borocalcite, mirabilite and soda ash according to the formula ratio, crushing the mixture, and passing the crushed mixture through a 200-fold 400-mesh sieve to obtain a mixture 1;

s2, putting the mixture 1 obtained in the step S1 into a kiln, stirring and melting at the melting temperature of 1610-;

s3, drawing the molten glass obtained in the step S2 at 1340-1380 ℃, and cooling to form glass fibers;

s4, coating the glass fiber obtained in the step S3 with the impregnating compound prepared in the application, wherein the rotating speed of a wire drawing machine is 2800 and 3300r/min, and obtaining a finished product.

Wherein, the raw materials in the step S1 include, by weight, 31.95% of silica sand, 26.84% of kaolin, 26.16% of calcite, 2.45% of fluorite, 11.97% of borocalcite, 0.26% of mirabilite, and 0.37% of soda ash.

The adding amount of the impregnating compound prepared in the step S4 is 0.09-0.15% of the weight of the glass fiber.

Compared with the prior art, the invention has the beneficial effects that:

(1) the glass fiber impregnating compound prepared by the method improves the uniformity of glass ingredients and the dispersion performance of glass fibers by optimizing the formula and the proportioning relation among the formulas, further improves the yield of the glass fibers, reduces the production cost, and the glass fibers prepared by the formula have more excellent fiber strength.

(2) The glass fiber impregnating compound is compounded by selecting proper components such as a film forming agent, a coupling agent, a lubricant, a pH value regulator, an antistatic agent and the like, and has excellent mechanical properties (bending strength and tensile strength), corrosion resistance, viscosity and protofilament attachment rate when used for impregnating glass fibers.

Detailed Description

For a better understanding of the present invention, the present invention is further described in conjunction with the following specific examples, wherein the terminology used in the examples is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.

The raw material sources are as follows:

the preservative is purchased from Daihu chemical industry Co., Ltd, and the product is FS-14D; the epoxy resin emulsion is purchased from Wuhansenjie chemical technology Co., Ltd, product number LS 255; the polyvinyl acetate emulsion was purchased from air products and chemicals, usa under the product designation Airflex 410; methacryloxypropyltrimethoxysilane was purchased from Nanjing Needt New Material technology, Inc., having a product designation of KH-570; gamma-chloropropyltrimethoxysilane is available from western chemical technology (Shandong) Inc. under the product designation 2530-87-2; the acrylate emulsion was purchased from Shandong flourishing China New materials Co., Ltd, product designation F257; dibutyl phthalate is purchased from Jiangyin Xinbo chemical Co., Ltd, and the product cargo number is DBP; the decaalkyl trimethyl ammonium chloride is purchased from Shanghai drum minister biotechnology limited company, and the product cargo number is 10108-87-9; polyethylene glycol 4000 is purchased from Haian petrochemical plants of Jiangsu province, and the product number is PEG 4000; stearic acid amide was purchased from Changsha Henchang chemical Co., Ltd, Hunan; product order number, chamid S;

the other raw materials are common commercial products, so that the source of the raw materials is not particularly limited.

Example 1

A glass fiber impregnating compound comprises the following raw materials in percentage by weight: 12% of epoxy resin emulsion, 18% of polyvinyl acetate emulsion, 0.6% of coupling agent, 0.9% of acetic acid, 5% of acrylate emulsion, 0.5% of dibutyl phthalate, 0.05% of alkyl trimethylammonium chloride, 0.2% of stearic acid, 2% of polyethylene glycol, 0.1% of fatty amide, 0.7% of ammonium chloride, 0.8% of preservative and the balance of deionized water.

The production method of the glass fiber infiltrated by the glass fiber infiltrating agent comprises the following steps:

s1, mixing 31.95% of silica sand, 26.84% of kaolin, 26.16% of calcite, 2.45% of fluorite, 11.97% of borocalcite, 0.26% of mirabilite and 0.37% of soda by weight percentage, crushing all the materials, and passing through a 200-mesh 400-mesh sieve to obtain a mixture 1;

s2, putting the mixture 1 obtained in the step S1 into a kiln, stirring and melting, wherein the melting temperature is 1610 ℃, and obtaining molten glass;

s3, drawing the molten glass obtained in the step S2 at 1380 ℃, and cooling to form glass filaments;

and S4, coating the glass fiber obtained in the step S3 with the prepared impregnating compound, wherein the adding amount of the impregnating compound is 0.15% of the weight of the glass fiber, and the rotating speed of a wire drawing machine is 2800r/min, so that a finished product is obtained.

Example 2

A glass fiber impregnating compound comprises the following raw materials in percentage by weight: 8% of epoxy resin emulsion, 18% of polyvinyl acetate emulsion, 2.1% of coupling agent, 0.3% of acetic acid, 5% of acrylate emulsion, 0.1% of dibutyl phthalate, 0.01% of alkyl trimethylammonium chloride, 0.8% of stearic acid, 0.5% of polyethylene glycol, 0.25% of fatty amide, 0.2% of ammonium chloride, 0.3% of preservative and the balance of deionized water.

s2, putting the mixture 1 obtained in the step S1 into a kiln, stirring and melting at 1680 ℃ to obtain molten glass;

s3, drawing the molten glass obtained in the step S2 at 1340 ℃, and cooling to form glass filaments;

and S4, smearing the glass fiber obtained in the step S3 with the prepared impregnating compound, wherein the adding amount of the impregnating compound is 0.09% of the weight of the glass fiber, and the rotating speed of a wire drawing machine is 3300r/min, so that a finished product is obtained.

Example 3

A glass fiber impregnating compound comprises the following raw materials in percentage by weight: 10% of epoxy resin emulsion, 15% of polyvinyl acetate emulsion, 1.2% of coupling agent, 0.6% of acetic acid, 8% of acrylate emulsion, 0.3% of dibutyl phthalate, 0.03% of alkyl trimethylammonium chloride, 0.5% of stearic acid, 1.5% of polyethylene glycol, 0.18% of fatty amide, 0.5% of ammonium chloride, 0.5% of preservative and the balance of deionized water.

s2, putting the mixture 1 obtained in the step S1 into a kiln, stirring and melting, wherein the melting temperature is 1650 ℃, and obtaining molten glass;

s3, drawing the molten glass obtained in the step S2 at 1360 ℃, and cooling to form glass filaments;

and S4, smearing the glass fiber obtained in the step S3 with the prepared impregnating compound, wherein the adding amount of the impregnating compound is 0.12% of the weight of the glass fiber, and the rotating speed of a wire drawing machine is 3000r/min, so that a finished product is obtained.

Example 4

A glass fiber impregnating compound comprises the following raw materials in percentage by weight: 11% of epoxy resin emulsion, 14% of polyvinyl acetate emulsion, 1.8% of coupling agent, 0.4% of acetic acid, 9% of acrylate emulsion, 0.4% of dibutyl phthalate, 0.05% of alkyl trimethylammonium chloride, 0.3% of stearic acid, 1.5% of polyethylene glycol, 0.25% of fatty amide, 0.6% of ammonium chloride, 0.7% of preservative and the balance of deionized water.

and S4, smearing the glass fiber obtained in the step S3 with the prepared impregnating compound, wherein the adding amount of the impregnating compound is 0.1% of the weight of the glass fiber, and the rotating speed of a wire drawing machine is 3000r/min, so that a finished product is obtained.

Example 5

A glass fiber impregnating compound comprises the following raw materials in percentage by weight: 9% of epoxy resin emulsion, 16% of polyvinyl acetate emulsion, 0.6% of coupling agent, 0.8% of acetic acid, 6% of acrylate emulsion, 0.2% of dibutyl phthalate, 0.02% of alkyl trimethylammonium chloride, 0.8% of stearic acid, 0.5% of polyethylene glycol, 0.15% of fatty amide, 0.3% of ammonium chloride, 0.4% of preservative and the balance of deionized water.

s2, putting the mixture 1 obtained in the step S1 into a kiln, stirring and melting, wherein the melting temperature is 1620 ℃, and obtaining glass liquid;

s4, smearing the glass fiber obtained in the step S3 with the prepared impregnating compound, wherein the adding amount of the impregnating compound is 0.13% of the weight of the glass fiber, and the rotating speed of a wire drawing machine is 3200r/min, so that a finished product is obtained.

Comparative example 1

The difference from the embodiment 3 is that the glass fiber impregnating compound comprises the following raw materials in percentage by weight: 6% of epoxy resin emulsion, 20% of polyvinyl acetate emulsion, 2.5% of coupling agent, 0.1% of acetic acid, 3% of acrylate emulsion, 0.05% of dibutyl phthalate, 0.1% of alkyl trimethylammonium chloride, 1.0% of stearic acid, 0.3% of polyethylene glycol, 0.35% of fatty amide, 0.1% of ammonium chloride, 1.2% of preservative and 65.3% of deionized water.

Other sources of raw materials and methods of producing glass fibers were the same as in example 3.

Comparative example 2

The difference from the embodiment 3 is that the glass fiber impregnating compound comprises the following raw materials in percentage by weight: 14% of epoxy resin emulsion, 10% of polyvinyl acetate emulsion, 0.4% of coupling agent, 1.3% of acetic acid, 12% of acrylate emulsion, 0.8% of dibutyl phthalate, 0.02% of alkyl trimethylammonium chloride, 0.1% of stearic acid, 2.2% of polyethylene glycol, 0.05% of fatty amide, 0.9% of ammonium chloride, 0.1% of preservative and 58.13% of deionized water.

Comparative example 3

The difference from example 3 of the present application is that the weight ratio of methacryloxypropyltrimethoxysilane to gamma-chloropropyltrimethoxysilane is 5:1 (wherein the total weight of methacryloxypropyltrimethoxysilane and gamma-chloropropyltrimethoxysilane is the same as in example 3).

Other sources and contents of raw materials and preparation method are the same as those of example 3.

Comparative example 4

The difference from example 3 of the present application is that the weight ratio of methacryloxypropyltrimethoxysilane to gamma-chloropropyltrimethoxysilane is 1.5:1 (wherein the total weight of methacryloxypropyltrimethoxysilane and gamma-chloropropyltrimethoxysilane is the same as in example 3).

Other sources and contents of raw materials and production method of glass fiber are the same as example 3.

Comparative example 5

The difference from example 3 of the present application is that the weight ratio of the epoxy resin emulsion and the polyvinyl acetate emulsion is 1:0.3 (wherein the total weight of the epoxy resin emulsion and the polyvinyl acetate emulsion is the same as that of example 3).

Comparative example 6

The difference from example 3 of the present application is that the weight ratio of the epoxy resin emulsion to the polyvinyl acetate emulsion is 1:2.6 (wherein the total weight of the epoxy resin emulsion and the polyvinyl acetate emulsion is the same as in example 3).

Comparative example 7

The difference from example 3 herein is that the weight ratio of polyethylene glycol, fatty amide and ammonium chloride is 6:1:0.5 (wherein the total weight of polyethylene glycol, fatty amide and ammonium chloride is the same as in example 3).

Comparative example 8

The difference from example 3 herein is that the weight ratio of polyethylene glycol, fatty amide and ammonium chloride is 18:1:22 (where the total weight of polyethylene glycol, fatty amide and ammonium chloride is the same as in example 3).

Comparative example 9

The difference from example 3 of the present application is that in the method for producing glass fibers impregnated with a glass fiber sizing agent, the amount of the sizing agent added in step S4 is 0.07% by weight of the glass filaments.

Comparative example 10

The difference from example 3 of the present application is that in the method for producing glass fibers impregnated with a glass fiber sizing agent, the amount of the sizing agent added in step S4 is 0.18% by weight of the glass filaments.

Comparative example 11

Example 2 in patent CN 109180009B.

Test experiments:

the above examples 1 to 5 and comparative examples 1 to 11 were applied to the production of glass fibers, and the respective properties of the glass fibers were tested, and the test results were as follows:

mechanical strength: the measurement was carried out using a tensile tester (model: YG 021E); modulus of elasticity: measuring Young's modulus by using a stretching method; and (3) viscosity testing: the detection method comprises the following steps: the viscosity of the sizing agent is measured by a Brookfield rotary viscometer at 40 +/-0.5 ℃.

Protofilament attachment rate:

definition of combustible content: the ratio of the mass of combustible material in the dried glass fibers to the mass of the dried glass fibers under specified conditions is expressed as a percentage.

The detection method comprises the following steps: the dried sample was burned at 625. + -. 20 ℃ under the standard temperature and temperature conditions to measure the mass.

The calculation method comprises the following steps: combustible content ═ W₁+W₂-W₃)/W₂×100％

In the formula: w₁-represents the weight of the crucible; w₂-the weight of the sample after drying; w₃Crucible and sample weight after hard firing.

Corrosion resistance: measuring the original average diameter of 45 glass fiber monofilaments randomly, soaking about 10g of glass fibers in a microetching solution for 1.5h at normal temperature (25 ℃), taking out the glass fibers, drying the glass fibers, measuring the average diameter of the soaked glass fibers again, subtracting the diameter of the soaked glass fibers from the diameter before soaking to obtain a difference value, and calculating the proportion of the difference value to the original average diameter to judge the corrosion resistance of the glass fibers; microetching liquid: adding 3mL of hydrogen peroxide H with the concentration of 30 percent into 100mL of pure water₂O₂And 3mL of 98% concentrated sulfuric acid to obtain microetching solution (H)₂O₂3％，H₂SO₄3％)。

Table 1:

as can be seen from the detection data in the above Table 1, the glass fiber soaked by the glass fiber impregnating compound prepared only by using the components disclosed by the invention and within the preferable proportion range of the invention has excellent performance and meets the standard requirements in the industry. The raw materials of comparative examples 1-2 in the table 1 are out of the protection range of the application, the weight ratio of the raw materials is changed in the comparative examples 3-8, the weight of the glass fiber infiltrated by the impregnating compound prepared by the invention is changed in the comparative examples 9-10, so that the weight ratio or the content is not in the preferred range of the application, and the change of the weight ratio or the content can influence the performance of the glass fiber; however, in view of the overall situation, the sizing agent impregnated glass fibers prepared by the formulation provided in the present application are obviously due to the properties of the glass fibers disclosed in the prior art.

Claims

1. A glass fiber impregnating compound is characterized in that:

the impregnating compound comprises the following raw materials: epoxy resin emulsion, polyvinyl acetate emulsion, coupling agent, acetic acid, acrylate emulsion, dibutyl phthalate, alkyl trimethylammonium chloride, stearic acid, polyethylene glycol, fatty amide, ammonium chloride, preservative and deionized water.

2. The sizing agent according to claim 1, wherein:

the impregnating compound comprises the following raw materials in percentage by weight: 8-12% of epoxy resin emulsion, 12-18% of polyvinyl acetate emulsion, 0.6-2.1% of coupling agent, 0.3-0.9% of acetic acid, 5-10% of acrylate emulsion, 0.1-0.5% of dibutyl phthalate, 0.01-0.05% of alkyl trimethylammonium chloride, 0.2-0.8% of stearic acid, 0.5-2% of polyethylene glycol, 0.1-0.25% of fatty amide, 0.2-0.7% of ammonium chloride, 0.3-0.8% of preservative and the balance of deionized water.

3. The sizing agent according to claim 1, wherein: the polyethylene glycol is one or more of polyethylene glycol 4000, polyethylene glycol 6000 and polyethylene glycol 3000.

4. The sizing agent according to claim 1, wherein: the alkyl trimethyl ammonium chloride is one or more of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.

5. The sizing agent according to claim 1, wherein: the fatty amide is one or more of N, N-dimethylpropyl erucamide, behenamide and stearic amide.

6. The sizing agent according to claim 1, wherein: the coupling agent is methacryloxypropyltrimethoxysilane and gamma-chloropropyltrimethoxysilane in a weight ratio of 3-1: 1.

7. The sizing agent according to claim 1, wherein: the weight ratio of the epoxy resin emulsion to the polyvinyl acetate emulsion is 1: 1-2.

8. The sizing agent according to claim 1, wherein: the weight ratio of the dibutyl phthalate to the alkyl trimethylammonium chloride is 10-35: 1.

9. The sizing agent according to claim 1, wherein: the weight ratio of the polyethylene glycol to the fatty amide to the ammonium chloride is 8-15:1: 1-20.

10. A method for producing size-impregnated glass fibers as defined in any one of claims 1 to 9, comprising the steps of:

s4, smearing the glass fiber obtained in the step S3 on the impregnating compound prepared in the application, and obtaining a finished product when the rotating speed of a wire drawing machine is 2800-;

the amount of the impregnating compound prepared in the step S4 is 0.09-0.15% of the weight of the glass fiber.