CN117486504A

CN117486504A - High-temperature starch type impregnating agent for electronic grade glass fiber yarns, and preparation method, product and application thereof

Info

Publication number: CN117486504A
Application number: CN202311438401.0A
Authority: CN
Inventors: 杨国明; 陈国卫; 方俊; 马哲; 王富峰; 王昱涵
Original assignee: Jushi Group Co Ltd
Current assignee: Jushi Group Co Ltd
Priority date: 2023-11-01
Filing date: 2023-11-01
Publication date: 2024-02-02

Abstract

The application discloses a high-temperature starch type impregnating compound for electronic-grade glass fiber yarns, which is an aqueous solution of active ingredients, wherein the solid content of the impregnating compound is 5.19-10.76%, and the solid mass of each active ingredient accounts for the total solid mass of the impregnating compound and is as follows: 3.40 to 7.00 percent of starch; 1.10 to 2.30 percent of grease; 0.05 to 0.10 percent of emulsifying agent; 0.15 to 0.40 percent of pretreatment agent A and 0.30 to 0.50 percent of pretreatment agent B; 0.17 to 0.40 percent of antistatic agent; ammonia water 0.02-0.06%. The starch is a mixture of high-amylose corn starch, acrylamide grafted modified starch and acetyl modified starch, and the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-5:2:1. The sizing agent can keep the advantages of high bundling property and good cladding property of the sizing agent yarn in a high-temperature system, reduce the stiffness of the yarn, improve the lubricity of the yarn, ensure that the D450 and D900 yarns are not easy to produce Mao Sansi in the production process, reduce the influence of production process fluctuation on the quality of the yarn, obviously improve the weaving performance of the yarn and obviously reduce the defects of cloth covers.

Description

High-temperature starch type impregnating agent for electronic grade glass fiber yarns, and preparation method, product and application thereof

Technical Field

The application relates to the technical field of glass fiber surface treatment agents, in particular to the technical field of production of impregnating compounds for electronic-grade glass fibers, and specifically relates to a high-temperature starch type impregnating compound for D450 and D900 electronic-grade glass fiber yarns, a preparation method, a product and application.

Background

With the revolution of information technology, digital power gradually goes into the stages of information processing and high speed and signal transmission and high frequency, so that the frequency of electronic equipment is becoming higher and higher for processing data which is increasing, electronic products are continuously developed in the directions of light weight, thinness and smallness, and High Density Interconnection (HDI) technology is also emerging. The electrical properties of the substrate seriously affect the characteristics of the digital circuit, so that the requirements of light weight, high density and multilayering are raised on the performance of the board.

The main application fields of the HDI board are high-end fields such as mobile phones, computers, systems, system back boards, automobile products and the like. In order to better meet the requirements of downstream markets, the glass fiber cloth industry is in need of developing cloth for 1080 and 106-specification HDI ultrathin plates, which is thinner and lighter than 7628 and 2116 thick cloth series, has higher electrical insulation property and can be laminated in larger number. 1080. Compared with 9 mu m G series yarns, the 5 mu m D450 and D900 yarns for the 106 ultrathin cloth have finer yarns, have higher requirements on production process, are easier to grind off single fibers in the processes of drawing and twisting, and have no improvement on production efficiency. In view of the above performance characteristics of the yarn, the sizing agent used for coating and producing the D450 and D900 yarns needs to be better than the G75 sizing agent in bundling property, coating property and lubricity so as to achieve the purpose of reducing yarn hairiness; at the same time, it is desirable to make the yarn softer and more uniform to improve its weaving properties.

The impregnating compound used for coating and producing D series yarn products in the industry is mainly a low-temperature system, the modified starch cost of the system is high, the consumption of the impregnating compound per ton yarn is high, the utilization rate of the impregnating compound in the wire drawing and coating process is low, nearly half of the impregnating compound can be thrown away, and only a small part of the impregnating compound can be effectively adsorbed on yarn bundles. Meanwhile, the production process of the D450 and D900 yarns has very severe requirements, not only requires the production environment to keep constant temperature and humidity, but also has the advantages of difficult overlarge wire drawing and twisting tension, low production speed and low production efficiency. The D450 yarn and the D900 yarn produced by using the low-temperature impregnating compound coating have a large amount of powder falling in the weaving process, so that main nozzles and auxiliary nozzles of the weaving are easily blocked, scaling on a weaving reed is easily caused, the weaving Mao San yarn appears, and the production efficiency is also affected. If the existing high-temperature system impregnating compound is directly adopted to produce yarns, the stiffness of the yarns is improved, and the yarns are not easy to fall off, but the weft yarns are bent and the cloth cover is uneven during weaving; meanwhile, the problems of tightness and warp fuzzing of the loom beam occur, so that the loom beam is also unfavorable for production and use.

In summary, development of a high-temperature system impregnating compound is needed to overcome the problems of poor wear resistance, severe production environment requirements, more production powder falling, low production efficiency, more cloth defects and the like of D450 and D900 yarns at the present stage.

Disclosure of Invention

The purpose of the application is to provide a high-temperature starch type impregnating compound for D450 and D900 electronic grade glass fiber yarns, and the impregnating compound is coated to produce the D450 and D900 electronic grade glass fiber yarns, so that the problems of high impregnating compound consumption, more hairiness, poor wear resistance, harsh process requirements and the like in the production process can be solved; the binding capacity with the yarn is increased, and meanwhile, the bundling property and the wear resistance of the yarn are improved. The D450 and D900 yarns produced by the sizing agent have excellent weaving performance, and the woven electronic cloth product is not easy to generate defects, and the cloth cover is light and thin and meets the requirement of subsequent processing.

According to one aspect of the application, a high-temperature starch type impregnating compound for electronic-grade glass fiber electronic yarns is provided, wherein the impregnating compound is an aqueous solution of an active ingredient, and the solid content of the impregnating compound is 5.19-10.76%, and the active ingredient comprises starch, grease, a pretreatment agent, an antistatic agent and ammonia water; the pretreatment agent comprises a pretreatment agent A and a pretreatment agent B; the solid mass of each active ingredient of the impregnating compound is expressed as follows in percentage of the total solid mass of the impregnating compound:

the starch is a mixture of high-amylose corn starch, acrylamide grafted modified starch and acetyl modified starch, and the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-5:2:1.

Wherein the solid content of the impregnating compound is 5.69-10.28%, and the solid mass of each active ingredient of the impregnating compound is expressed as the following percentage of the total solid mass of the impregnating compound:

the starch is a mixture of high-amylose corn starch, acrylamide grafted modified starch and acetyl modified starch, and the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-4:2:1.

Wherein the high linear chain content of the high linear chain corn starch is 40-65%; the substitution degree of the acrylamide grafted modified starch is 0.02-0.20%, and the substitution degree of the acetyl modified starch is 0.06-0.10%.

Wherein the grease is mixed grease of hydrogenated modified soybean phosphate grease and water-based paraffin oil or mixed grease of hydrogenated peanut grease and water-based paraffin oil. .

Wherein, the paraffin content of the water-based paraffin oil is 60-85 percent, and the melting point is 40-50 ℃; and the water-based paraffin oil accounts for 13-24% of the total mass of the mixed grease.

Wherein the emulsifier is at least one of polyurethane, N-dodecylmethylamine and polyvinyl alcohol.

Wherein the pretreatment agent A comprises glycerol or/and polyethylene glycol; the pretreatment agent B comprises at least one of decyl glycidyl ether, tri (1, 2-epoxy) propyl ether and higher unsaturated fatty glyceride.

Wherein the antistatic agent comprises at least one of alkyl dihydroxyethyl ammonium acetate, ethoxyl lauramide and glycerol stearate.

Wherein the starch is required to be polished by an ultrafine grinder, and the polishing requirement is that the passing rate of a screen with fineness of 50 meshes is more than 99.0 percent.

The action and the content of each component in the high-temperature starch type impregnating compound of the electronic-grade glass fiber electronic yarn are described as follows:

the starch of the present application is a mixture of high amylose corn starch, acrylamide grafted modified starch and acetyl modified starch. The high-amylose corn starch has good film forming effect, can form a flexible starch film, has stable mechanical property under high relative humidity, but has low gelatinization degree, quick starch aging and quick molecular aggregation; although the film forming effect of the acrylamide grafted modified starch is poor, the starch is easy to gelatinize, so that the defect of poor stability of high-amylose starch can be overcome, the retrogradation phenomenon of the sizing agent is reduced, the dispersion capacity of the starch sizing agent in emulsion can be improved, and the uniformity of coating of the sizing agent is improved; the acetyl modified starch has high gelatinization degree, can increase the gel state of starch slurry, improves the tensile strength of a starch film, has good coating property on yarns, and can improve the wear resistance of the yarns. Experiments show that the three kinds of starch are matched with each other for use, so that the coating property of the starch on the yarns can be improved, the formed starch film is not easy to rub and damage, the smoothness of the yarns is improved in the processing and use process, and the generation of fuzzing caused by mechanical abrasion is prevented. Further, the application regulates the use performance of the sizing agent by controlling the mass ratio of the three starches, wherein the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-5:2:1, and preferably, is 1:1:1-4:2:1. Experiments show that if high amylose starch is used too much, the yarn is easy to fall off, starch slurry is easy to retrograde, and the quality guarantee period of the impregnating compound is shortened; too little usage can lead to softer yarns and increased impregnating compound consumption. In the application, the acrylamide grafted modified starch and the acetyl modified starch are used in a mixed mode according to the mass relation of 1:1-2:1, so that the acrylamide grafted modified starch and the acetyl modified starch have complementary functions, the film forming effect of the starch is improved, and a starch film is not easy to rub and damage. Wherein, the proportion of the acrylamide grafted modified starch can be properly increased, and the effect of reducing the slurry retrogradation phenomenon can be achieved; the acetyl modified starch is not suitable to be added too much, and if the addition amount of the acetyl modified starch is too much, the yarn is sticky, so that the subsequent production and use are not facilitated.

In addition, the starch dosage used in the method needs to be controlled in a certain range, if the adding amount is too large, the sizing agent cannot be fully coated on the yarns, the sizing agent is low in utilization rate, most of the sizing agent is wasted, the bonding effect of the sizing agent cannot be increased only by increasing the starch dosage, and the yarn powder falling in the weaving process is increased, so that the production and the use are not facilitated; too little amount is used, the smoothness of the yarn is reduced, and the production and the use are also not facilitated. Thus, the solids mass of the starch is controlled in this application to be 3.4 to 7.0%, preferably 3.80 to 7.0%, more preferably 3.9 to 6.5% of the total solids mass of the sizing agent.

The present application controls the linear content in the high amylose corn starch to be 40-65%, preferably 55-60%. If the linear chain content of the high-amylose corn starch is too high, the sizing agent is poor in stability, the starch is not easy to gelatinize, and the sizing agent is easy to delaminate; if the linear chain content is too low, the bundling effect cannot be achieved. Meanwhile, the substitution degree of the acrylamide grafted modified starch and the acetyl modified starch needs to be controlled in a proper range, and too low substitution degree is incomplete modification, so that the reaction conversion rate is low, the amount of unmodified starch is increased, the effect of modifying the starch cannot be achieved, and the gelatinization degree of starch slurry is reduced; the high degree of substitution can also function, but the production cost is increased. The substitution degree of the acrylamide grafted modified starch is 0.02-0.20%, the substitution degree of the acetyl modified starch is 0.06-0.10%, preferably, the substitution degree of the acrylamide grafted modified starch is 0.05-0.15%, and the substitution degree of the acetyl modified starch is 0.08-0.10%.

Pretreatment of starch slurry using a pretreatment agent is an important point in the present application. If the starch slurry is directly cooked without pretreatment, the bonding capability of the sizing film and the surface of the glass fiber is reduced, and the powder falling is increased. The pretreatment agent can react with active groups of starch in the cooking process, so that the binding capacity between starch molecules and between starch and the surface of glass fiber is improved, and the soaking capacity is improved. The treated sizing agent can effectively reduce the brittleness of the starch film and the bonding of the precursor and the filament winding tube layer, and can improve the wrapping effect of the sizing agent on the glass fiber yarns. D450, D900 as 5 μm glass fiber yarns, the individual fibers are easily broken and not easily gathered together, while all tows are needed to be gathered together in the drawing process, if the sizing agent and the tows cannot be well combined and wrapped, the sizing agent and the tows can contact with process accessories to generate fuzzing.

The pretreatment agent is a mixture of a pretreatment agent A and a pretreatment agent B, and the pretreatment agent A can soften a starch film and improve plasticity; the pretreatment agent B can be combined with starch and glass fiber in a chemical bond form, can improve the impregnating capacity of the impregnating compound, and can help to improve the strength of the yarn. Preferably, the pretreatment agent A is glycerol or/and polyethylene glycol; the pretreatment agent B is at least one of middle decyl glycidyl ether, glycerol tri (1, 2-epoxy) propyl ether and higher unsaturated fatty glyceride. Meanwhile, the dosage of the pretreatment agent A and the pretreatment agent B needs to be controlled in a proper range; experiments show that if the dosage of the pretreatment agent A is too large, the strength of the film is reduced and then the film is broken, so that the effect of coating the glass fiber yarns can not be achieved; if the amount is too small, the abrasion resistance of the yarn is deteriorated and hairiness is increased. The excessive amount of the pretreatment agent B can lead to yarn lamination, and the yarn is difficult to unwind when the precursor is twisted; the required effect cannot be achieved if the dosage is too small. Thus, the application controls the amount of the pretreatment agent A (solid mass) to be 0.15 to 0.40%, preferably 0.20 to 0.40%, more preferably 0.25 to 0.30% of the total solid mass of the impregnating compound; the solid mass of the pretreatment agent B accounts for 0.30-0.50% of the total solid mass of the impregnating compound, preferably 0.30-0.46%, and more preferably 0.30-0.40%.

The grease is a bridge for attaching starch to the glass fiber, and can also enable other components of the impregnating compound to be dissolved in the emulsion of water and oil. The grease is preferably mixed grease of hydrogenated modified soybean phosphate grease and water-based paraffin oil or mixed grease of hydrogenated peanut grease and water-based paraffin oil, and the water-based paraffin oil accounts for 13-24% of the total mass of the mixed grease.

The adoption of the aqueous paraffin oil is another key point of the application, the paraffin oil can provide certain bundling property, the lubrication effect is increased, broken filaments can be flexible, and the broken filaments can be wrapped below the film. Compared with hydrogenated vegetable oil, the paraffin oil is added, and the grey cloth is easy to desize after smoldering. Wherein, the paraffin content in the aqueous paraffin oil is 60-85%, the melting point is 40-50 ℃, the melting point is required to be dissolved in hot water, and the aqueous paraffin oil is not easy to be re-coagulated into blocks after being dissolved.

The emulsifier is mainly used for emulsifying the hydrogenated oil. The emulsifier described herein is preferably at least one of polyurethane, N-dodecylmethylamine and polyvinyl alcohol. Polyurethane and polyvinyl alcohol can provide better emulsification effect, and if N-dodecylmethylamine is added at the same time, grease can be better dispersed, and the emulsification effect is improved. The usage amount of the emulsifier needs to be matched with the oil amount, the usage amount is too small, and the emulsification is insufficient; excessive amounts can result in waste. The solid mass of the emulsifier is controlled to be 0.05-0.10 percent, preferably 0.06-0.08 percent of the total solid mass of the impregnating compound.

For the yarns with small diameter of the D450 and D900 single fibers, electricity is easily generated by friction with air and equipment in the processing and using process, and the requirements on temperature and humidity are strict, so that a certain amount of antistatic agent needs to be added into the sizing agent. In the present application, the antistatic agent is preferably at least one of alkyl dihydroxyethyl ammonium acetate, ethoxyl lauramide and glycerol stearate. The addition amount of the antistatic agent is small, the effect of static electricity removal cannot be achieved, and the phenomenon of scattered softness of yarns can occur due to the fact that the addition amount is too large. The solid mass of the antistatic agent is controlled to be 0.17-0.40%, preferably 0.21-0.36%, more preferably 0.26-0.33% of the total solid mass of the sizing agent.

In the application, the ammonia water can adjust the pH value of the impregnating compound, so that the pH value of the impregnating compound is neutral or weak acid, and the stability of the impregnating compound is improved.

The water in this application acts as a dispersed phase of the components of the size, preferably deionized water.

In the present application, the solid mass of the emulsion is the mass of the rest of the emulsion after the emulsion is dried under a certain condition to remove water.

According to a second aspect of the present application, there is provided a method for preparing the high temperature starch type impregnating compound for electronic grade glass fiber yarns, which specifically comprises the following steps:

configuration of starch slurry: mixing the three starches according to the mass ratio, adding water accounting for 2-5% of the total mass of the sizing agent, and processing to the required fineness by an ultrafine grinder; adding the crushed starch and the pretreatment agent into warm water with the total mass of 10-20% of the impregnating compound, stirring and dispersing uniformly, steaming through a high-pressure reactor, mixing with normal-temperature water in equal proportion after steaming, and cooling to prepare starch slurry;

preparing an emulsion: adding grease into hot water with the total mass of 5-10% of the impregnating compound, melting, mixing with the emulsifying agent after melting, and emulsifying and dispersing to the required granularity;

configuration of antistatic agent solution: dissolving an antistatic agent in normal-temperature water accounting for 5-10% of the total mass of the sizing agent, and stirring until the antistatic agent is uniform;

preparing a sizing agent: mixing the prepared emulsion, antistatic agent solution and starch slurry, supplementing the residual water, and finally adding ammonia water.

In the above operation, the superfine starch grinding process should be carried out before the high-temperature cooking of the starch, and the other steps are carried out in different order.

Preferably, in the step of preparing the starch slurry, the crushed starch and the pretreatment agent are put into water at a temperature of 15-30 ℃.

Preferably, in the preparation step of the starch slurry, the cooking flow is 2000-3000 kg/h, and the cooking is carried out by a multi-tube high-pressure reactor, and the cooking temperature is setThe cooking pressure is set to be 2-5 kgf cm at the temperature of 110-130 DEG C ² 。

Preferably, in the step of preparing the starch slurry, the starch solution after the completion of the cooking is mixed with 2000-3000 kg/h of water at a mass ratio of 1:1 and cooled to prepare the starch slurry.

Preferably, in the step of preparing the emulsion, the temperature of the hot water is controlled to be 65-75 ℃, the emulsification and dispersion are carried out by adopting a high-low double-blade high-speed dispersing machine, the particle size is required to be tested after the emulsification, and the dispersion is stopped after the emulsification is qualified.

Preferably, the particle size of the dispersed emulsion is controlled to be 2-5 μm.

Preferably, in the antistatic agent preparing step, the temperature of the normal temperature water is controlled to be 15-30 ℃.

Among them, the crushing of starch to smaller fineness is an important point in the present application. The fineness of starch can influence the adhesion condition of the sizing agent on the precursor, the fineness of starch raw materials is generally 100-150 meshes, and for D450 and D900, starch particles with smaller fineness can enable the prepared sizing agent to be more easily adhered to the surface of glass fibers, so that the coverage rate is higher and more uniform. Starch particles with larger particles can lead to a rough surface of the glass fiber, which is unfavorable for uniformly coating the surface of the yarn. When the fineness is greater than 99.0% and the passing rate of the 50-mesh screen is greater than 99.0%, the uniformity of the impregnating compound is better, and the consumption of the impregnating compound is reduced.

The pretreatment of the starch slurry prior to cooking with a pretreatment liquid is a further important point of the present application. The pretreatment agent can be combined with active groups of two modified starches in a reaction manner in a high-temperature cooking process, so that the combination capacity of starch molecules and between starch molecules and glass fibers is improved, the plasticity and the permeability of a sizing agent film are improved, broken filaments caused by friction can be wrapped, the generation of hairiness is reduced, and meanwhile, the combination force of the starch molecules and the glass fiber surfaces can be improved, so that yarns are not easy to fall off in the production process.

According to a third aspect of the present application, there is provided a D450, D900 electronic grade glass fiber product produced from the aforementioned electronic grade glass fiber yarns coated with a high temperature starch size.

According to a fourth aspect of the present application there is provided the use of the aforementioned electronic grade glass fiber product in the digital power field.

The method improves the film forming performance of the sizing agent, increases the bonding capacity of the sizing agent and the glass fiber, and improves the bundling property and the wear resistance of the yarn by using the sizing agent. The yarn produced by using the sizing agent has excellent weaving performance and is not easy to generate defects.

Detailed Description

For the purposes of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below in conjunction with specific embodiments of the present application, and it is apparent that the described embodiments are some, but not all, embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be arbitrarily combined with each other.

The embodiments and the components and features in the embodiments can be combined with each other at will, and in the preferred embodiments, only the embodiments are included, and all the components and the combinations of the components are included in the protection scope of the present application.

Preferred example one:

the high-temperature starch type impregnating compound for the electronic grade glass fiber yarn comprises an effective component and water, wherein the solid content of the impregnating compound is 5.19-10.76%, and the effective component comprises starch, grease, an emulsifying agent, a pretreatment agent, an antistatic agent and ammonia water; the pretreatment agent comprises a pretreatment agent A and a pretreatment agent B; the solid mass of each active ingredient of the impregnating compound is expressed as follows in percentage by total solid mass of the impregnating compound:

the starch is a mixture of high-amylose corn starch, acrylamide grafted modified starch and acetyl modified starch, and the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-5:2:1; the pretreatment agent A is glycerol or/and polyethylene glycol; the pretreatment agent B is at least one of decyl glycidyl ether, tri (1, 2-epoxy) propyl ether and higher unsaturated fatty glyceride.

Preferred example two

The high-temperature starch type impregnating compound for the electronic grade glass fiber yarn comprises an effective component and water, wherein the solid content of the impregnating compound is 5.19-10.76%; wherein the effective components comprise starch, grease, an emulsifying agent, a pretreatment agent, an antistatic agent and ammonia water, and the pretreatment agent comprises a pretreatment agent A and a pretreatment agent B; the solid mass of each active ingredient of the impregnating compound is expressed as follows in percentage by total solid mass of the impregnating compound:

the starch is a mixture of high-amylose corn starch, acrylamide grafted modified starch and acetyl modified starch, and the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-4:2:1; the high-amylose corn starch has a high linear content of 40 to 65%, the acrylamide grafted modified starch has a degree of substitution of 0.02 to 0.20%, and the acetyl modified starch has a degree of substitution of 0.06 to 0.10%.

Preferred examples three

the starch is a mixture of high-amylose corn starch, acrylamide grafted modified starch and acetyl modified starch, and the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-4:2:1; the linear chain content of the high-amylose corn starch is 55-60%, the substitution degree of the acrylamide grafted modified starch is 0.05-0.15%, and the substitution degree of the acetyl modified starch is 0.08-0.10%;

the grease is mixed grease of hydrogenated modified soybean phosphate grease and water-based paraffin oil, wherein the water-based paraffin oil accounts for 13-24% of the total mass of the mixed grease;

the pretreatment agent A is glycerol or/and polyethylene glycol; the pretreatment agent B is at least one of decyl glycidyl ether, tri (1, 2-epoxy) propyl ether and higher unsaturated fatty glyceride.

Preferred example four

The high-temperature starch type impregnating compound for the electronic grade glass fiber yarn comprises an effective component and water, wherein the solid content of the impregnating compound is 5.69-10.28%; wherein the effective components comprise starch, grease, an emulsifying agent, a pretreatment agent, an antistatic agent and ammonia water, and the pretreatment agent comprises a pretreatment agent A and a pretreatment agent B; the solid mass of each active ingredient of the impregnating compound is expressed as follows in percentage by total solid mass of the impregnating compound:

wherein the starch is a mixture of high-amylose corn starch, acrylamide grafted modified starch and acetyl modified starch, and the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-5:2:1; the high-amylose content of the high-amylose corn starch is 40-65%, the substitution degree of the acrylamide grafted modified starch is 0.02-0.20%, and the substitution degree of the acetyl modified starch is 0.06-0.10%;

Preferred example five

wherein the starch is a mixture of high-amylose corn starch, acrylamide grafted modified starch and acetyl modified starch, and the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-4:2:1; the high-amylose content of the high-amylose corn starch is 40-65%, the substitution degree of the acrylamide grafted modified starch is 0.02-0.20%, and the substitution degree of the acetyl modified starch is 0.06-0.10%;

Preferred example six

the starch is a mixture of high-amylose corn starch, acrylamide grafted modified starch and acetyl modified starch, and the mass ratio of the high-amylose corn starch to the acrylamide grafted modified starch to the acetyl modified starch is 1:1:1-5:2:1; the high-amylose content of the high-amylose corn starch is 55-60%, the substitution degree of the acrylamide grafted modified starch is 0.05-0.15%, and the substitution degree of the acetyl modified starch is 0.08-0.10%;

Preferred examples seven

The high-temperature starch type impregnating compound for the electronic grade glass fiber yarn comprises an effective component and water, wherein the solid content of the impregnating compound is 6.29-9.36%; wherein the effective components comprise starch, grease, an emulsifying agent, a pretreatment agent, an antistatic agent and ammonia water, and the pretreatment agent comprises a pretreatment agent A and a pretreatment agent B; the solid mass of each active ingredient of the impregnating compound is expressed as follows in percentage by total solid mass of the impregnating compound:

The preparation method of each preferable example impregnating compound comprises the following steps:

configuration of starch slurry: mixing the three starches according to the mass ratio, adding water accounting for 2-5% of the total mass of the sizing agent, and processing to the required fineness by an ultrafine grinder; adding the crushed starch and the pretreatment agent into 15-30 ℃ water accounting for 10-20% of the total mass of the sizing agent, stirring and dispersing uniformly, then steaming through a high-pressure reactor, mixing with 2000-3000 kg/h of water at a mass ratio of 1:1 after steaming, and cooling to prepare starch slurry; the cooking flow is 2000-3000 kg/h, and the cooking is carried out by a multi-tube type high-pressure reactor, the cooking temperature is set to be 110-130 ℃, and the cooking pressure is set to be 2-5 kgf cm ² ；

Preparing an emulsion: adding grease into 65-75 ℃ water accounting for 5-10% of the total mass of the impregnating compound, melting, mixing with the emulsifying agent after melting, and emulsifying and dispersing to granularity of 2-5 mu m;

configuration of antistatic agent solution: dissolving an antistatic agent in 15-30 ℃ water accounting for 5-10% of the total mass of the impregnating compound, and stirring until the antistatic agent is uniform;

In order to better explain the technical scheme of the application, the following is a list of some specific examples 1-12 of the high temperature starch type impregnating compound for electronic grade glass fiber yarns, wherein the specific formulation of each component of the examples 1-12 is shown in table 1.

Table 1 sizing formulation of each example

Table 1 (follow-up) impregnating compound formulations of examples

Wherein, in examples 1 to 12, the high linear chain content of the high linear chain corn starch is 40 to 65%. The substitution degree of the acrylamide grafted modified starch is 0.02-0.20%, and the substitution degree of the acetyl modified starch is 0.06-0.10%. The preparation method of the impregnating compound of each embodiment is the same as that of the preferred example impregnating compound. In order to further embody the beneficial effects of the application, the properties of the D450 and D900 products produced by the conventional impregnating compound are selected as comparison examples, and are compared with the properties of the products of the specific embodiments of the application.

Comparative example 1:

the impregnating compound comprises effective components and water, the solid content is 6.0%, and the solid mass of each effective component accounts for the total solid mass of the impregnating compound and is expressed as follows:

wherein the substitution degree of the esterified modified amylopectin is 0.15-0.20%, and the substitution degree of the etherified modified amylopectin is 0.10-0.15%.

Comparative example 2:

the impregnating compound comprises effective components and water, the solid content is 6.4%, and the solid mass of each effective component accounts for the total solid mass of the impregnating compound and is expressed as follows:

wherein the substitution degree of the hydroxyethyl modified amylopectin is 0.05-0.15%, and the substitution degree of the etherified modified amylopectin is 0.10-0.20%.

The preparation method of the comparative examples 1-2 comprises the following steps:

1. controlling the concentration of starch according to the mass ratio of 10-20%, adding the starch into water with the mass ratio, stirring and dispersing uniformly, heating to 85-99 ℃ and steaming for 60 minutes, slowly adding normal-temperature water with the mass ratio of 10-20% into the mixture after steaming, and cooling;

2. adding grease and an emulsifying agent, adding hot water with the mass ratio of 10-20% of the sizing agent, controlling the temperature of the hot water to be 60-70 ℃, emulsifying for 30 minutes by high-speed stirring, adding additives such as an antistatic agent and the like into the emulsion, and stirring for 30-60 minutes to prepare the emulsion;

3. adding the prepared emulsion into starch slurry, supplementing the residual water, and finally adding ammonia water and uniformly stirring.

Comparative example 3:

the impregnating compound comprises effective components and water, the solid content is 8.72%, and the solid mass of each effective component accounts for the total solid mass of the impregnating compound and is expressed as follows:

starch: high amylose corn starch 0.8%, acrylamide grafted modified starch 1.5%, acetyl modified starch 3.2%;

grease: 1.7% of hydrogenated modified soybean phosphate grease and 0.4% of aqueous paraffin oil;

emulsifying agent: polyurethane 0.06%;

pretreatment agent A: glycerol 0.16% and polyethylene glycol 0.04%;

pretreatment agent B: decyl glycidyl ether 0.13%, glycerol tris (1, 2-epoxypropyl) ether 0.1% and higher unsaturated fatty acid glyceride 0.1%;

antistatic agent: 0.1% of alkyl dihydroxyethyl ammonium ethyl inner salt and 0.2% of polydimethylsiloxane;

ammonia water 0.05%;

preparation method reference is made to the preparation method of the impregnating compound of the examples.

Comparative example 4:

the formulation of comparative example 4 was the same as the composition of example 5 except that the pretreatment agent was not included, and the solid content was 7.6%.

The preparation method of comparative example 4 does not include a step of steaming the starch slurry with a pretreatment agent, and does not include a step of subjecting the starch to an ultra fine pulverizer processing, and the remaining process is the same as comparative example 3.

And (3) detecting production performance:

in the present application, the impregnating compounds of examples 1 to 12 and comparative examples 1 to 4 were subjected to production tests, D450 and D900 were only different in the fractional drawing number and the number, and the remaining production processes were identical, and 1000 cops were produced in each example. The process parameters are shown in Table 2.

Table 2 production process parameters

Wire drawing machine head rotating speed (r/min)	3400～3600
		Oiling linear velocity (m/min)	16～20
Impregnating compound application temperature (. Degree. C.)	55～65
		Twist (twist/m)	32～38
Twisting machine spindle speed (rpm/min)	2000～4500
		Twisting temperature (. Degree. C.)	20～30
Twist humidity (%)	35～60
		Loom rotation speed (rpm/min)	600～750

Wherein, to better illustrate the effect of the application, the comparative examples are consistent with the production process parameters of the examples. The yarn test method adopts GB/T7690 reinforcing material yarn test method, GB/T9914 reinforcing product test method, FZ/T01058-1999 yarn abrasion resistance test method reciprocating grinding roller method, the powder falling amount of the woven cloth is compared by placing a closed square box in a yarn beating-up path to collect data of one day, and the test result is shown in Table 3.

Table 3 test results of examples and comparative examples

The performance test results in Table 3 show that the D450 and D900 electronic grade glass fiber yarns produced by using the high temperature starch type sizing agent for the electronic grade glass fiber yarns in examples 1 to 12 of the application contain 1.25 to 1.36 percent of oil, 0.02 to 0.06 percent of water and have a twist of 32.2 to 35.8 twists/m. In the performance aspect of the examples, the cop breakage rate is 0.9-1.9%, which is obviously reduced compared with comparative examples 1-4. The cop hairiness rate of the embodiment is between 0.3 and 1.3 percent, and compared with the comparative examples 1 to 4, the hairiness quantity of the glass fiber yarn is obviously reduced. The abrasion resistant times of the embodiment of the application are between 56 and 70 times, which are far higher than those of the comparative example, and the yarn of the embodiment of the application is more abrasion resistant. The amount of the powder falling of the woven cloth in the embodiment of the application is 11.5-14.5 mg/d, and the powder falling is obviously smaller than that of each comparative example. In addition, the examples are not easy to scale when weaving, so that defects are caused, the defects of the cloth cover are 11.8-21.0/ten-thousand meters, and compared with comparative examples 1-4, the defects of the weaving are nearly doubled, so that the examples are more suitable for weaving production and application compared with comparative examples. The electronic grade glass fiber yarn produced by the high-temperature starch type impregnating compound for the D450 and D900 electronic grade glass fiber yarns has low hairiness and breakage rate, uniform and flexible yarns, less fabric powder falling and fewer fabric defects.

In summary, the formula and the preparation process of the high-temperature starch type impregnating compound for the D450 and D900 electronic grade glass fiber yarns are scientific and reasonable, and all components in the formula are matched with each other, so that the problems of Mao Yugao, non-wear-resistant yarns, more fabric powder falling, high fabric defects and the like of a D450 and D900 low-temperature system formula can be solved. Therefore, the method has important significance in the aspect of product quality upgrading.

Finally, it should be noted that: in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.

The above embodiments are only for illustrating the technical solution of the present application, and are not limiting. Although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims

1. The high-temperature starch type impregnating compound for the electronic grade glass fiber yarns is an aqueous solution of an active ingredient, and is characterized in that the solid content of the impregnating compound is 5.19-10.76%, wherein the active ingredient comprises starch, grease, a pretreatment agent, an antistatic agent and ammonia water; the pretreatment agent comprises a pretreatment agent A and a pretreatment agent B; the solid mass of each active ingredient of the impregnating compound is expressed as follows in percentage of the total solid mass of the impregnating compound:

2. The sizing agent according to claim 1, wherein the solid content of the sizing agent is 5.69-10.28%, and the percentage of the solid mass of each active ingredient of the sizing agent to the total solid mass of the sizing agent is expressed as follows:

3. The sizing agent according to claim 1 or 2, wherein the high-amylose corn starch has a high linear content of 40 to 65%; the substitution degree of the acrylamide grafted modified starch is 0.02-0.20%, and the substitution degree of the acetyl modified starch is 0.06-0.10%.

4. The sizing agent according to claim 1 or 2, wherein the grease is a mixed grease of hydrogenated modified soybean phosphate grease and aqueous paraffin oil or a mixed grease of hydrogenated peanut grease and aqueous paraffin oil.

5. The sizing agent according to claim 4, wherein the aqueous paraffin oil has a paraffin content of 60 to 85% and a melting point of 40 to 50 ℃; and the water-based paraffin oil accounts for 13-24% of the total mass of the mixed grease.

6. The sizing of claim 1 or 2, wherein the emulsifier is at least one of polyurethane, N-dodecylmethylamine, polyvinyl alcohol.

7. The sizing of claim 1 or 2, wherein the pretreatment a comprises glycerol or/and polyethylene glycol; the pretreatment agent B comprises at least one of decyl glycidyl ether, tri (1, 2-epoxy) propyl ether and higher unsaturated fatty glyceride.

8. The sizing of claim 1 or 2, wherein the antistatic agent comprises at least one of alkyl dihydroxyethyl ammonium acetate, ethoxylauramide, glycerol stearate.

9. The sizing of any of claims 1-8, wherein the starch is to be ground by an ultra-fine grinder, the grinding being required to have a fineness of 50 mesh screen passing of greater than 99.0%.

10. The method of preparing a sizing agent according to any one of claims 1 to 8, comprising the steps of:

preparing an emulsion: adding grease into hot water with the total mass of 5-10% of the impregnating compound, melting, mixing with an emulsifying agent after melting, and emulsifying and dispersing to the required granularity;

11. A D450, D900 electronic grade glass yarn product produced by the size coating of any one of claims 1 to 8.

12. Use of an electronic grade glass yarn product according to claim 11 in the digital electrical field.