CN112830689A - Impregnating compound for low-dielectric glass fiber direct roving and preparation method thereof - Google Patents
Impregnating compound for low-dielectric glass fiber direct roving and preparation method thereof Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 39
- 239000000839 emulsion Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 239000000314 lubricant Substances 0.000 claims description 96
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000003085 diluting agent Substances 0.000 claims description 36
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 29
- 239000007822 coupling agent Substances 0.000 claims description 19
- 238000004513 sizing Methods 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- 206010020112 Hirsutism Diseases 0.000 abstract description 16
- 238000005452 bending Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
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- 238000009941 weaving Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 230000001808 coupling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/465—Coatings containing composite materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/36—Epoxy resins
Abstract
The invention relates to the technical field of glass fiber impregnating compounds, in particular to an impregnating compound for direct roving of low-dielectric glass fibers and a preparation method thereof. The composition is prepared from the following components: the coating agent consists of a low-molecular-weight bisphenol A epoxy resin emulsion and a medium-molecular-weight bisphenol A epoxy resin emulsion, wherein the molecular weight range of the bisphenol A epoxy resin in the low-molecular-weight bisphenol A epoxy resin emulsion is 300-450, and the molecular weight range of the bisphenol A epoxy resin in the medium-molecular-weight bisphenol A epoxy resin emulsion is 1000-1400. The invention can reduce the hairiness of the low-dielectric glass fiber direct yarn, improve the yarn quality, is not easy to generate sanding in the weaving process, improves the yarn quality, improves the bundling property of the yarn, increases the flexibility of the yarn, improves the tensile strength and the bending strength of the yarn, and enhances the interface bonding force with resin.
Description
Technical Field
The invention relates to the technical field of glass fiber impregnating compounds, in particular to an impregnating compound for direct roving of low-dielectric glass fibers and a preparation method thereof.
Background
The size plays an all-important role in the drawing process of glass fibers. The glass fiber winding machine can bundle hundreds of glass fiber monofilaments into strand precursor, and the precursor is not mutually bonded after being wound into a precursor tube, so that the precursor can keep soft in the spinning process, the mechanical abrasion is reduced, and various processing performances and application characteristics of glass fiber products are endowed. The development of glass fiber is nowadays similar to the varieties of the glass fiber with full meshes, and the glass fiber also has wide application fields, and depends on the key functions of continuous improvement of the quality of the impregnating compound and continuous increase of the varieties to some extent.
Since the birth of the last fifties of the last century, glass fiber factories in China continue to use original Susan paraffin emulsion as a drawing sizing agent until the middle seventies, and the glass fiber factories in China adopt the paraffin emulsion as a drawing sizing agent for drawing textile glass fibers or reinforced glass fibers. Most foreign impregnating compounds are special for one dose, even the special impregnating compound is customized according to the special requirements of a certain user, but one dose is multiple in China and is not changed for years. The hardness, bundling property, banding property, dispersibility and smoothness of the textile yarn and the reinforcing yarn do not meet the quality standard, and the technical performance requirements of deep processing and textile and reinforcing glass fiber products can not be met. Therefore, the impregnating compound has been a research subject to be solved for a long time and restricts the improvement of the industrial yield and quality of the glass fiber and the development of varieties in China.
The low dielectric glass fiber (D glass for short) is a special glass fiber with low density, low dielectric constant, low dielectric loss and small influence of the change of the dielectric property such as temperature, frequency and the like, is an ideal material with wide frequency band and high wave transmission, and is widely applied to the fields of radomes, electromagnetic windows, stealths, printed circuit boards and the like.
The yarn produced by the impregnating compound for the low-dielectric glass fiber direct yarn at present has poor bundling property, is slightly hard, has more hairiness, has poor interface combination with resin, and can not meet the market demand.
Disclosure of Invention
The first object of the present invention is to provide a sizing agent for low dielectric glass fiber direct roving, which can improve the bundling property and flexibility of the low dielectric glass fiber direct roving, reduce hairiness, increase the compatibility with a matrix resin material, and improve the interface bonding force between the yarn and the resin. The second purpose of the invention is to provide a preparation method of the impregnating compound for the direct roving of the low-dielectric glass fiber.
The invention provides a sizing agent for direct roving of low-dielectric glass fibers, which is prepared from the following components: the coating comprises a film forming agent, a lubricant, a coupling agent, a pH regulator and deionized water, wherein the film forming agent is composed of a low-molecular-weight bisphenol A epoxy resin emulsion and a medium-molecular-weight bisphenol A epoxy resin emulsion, and the molecular weight range of bisphenol A epoxy resin in the low-molecular-weight bisphenol A epoxy resin emulsion is as follows: 300-450, the molecular weight range of the bisphenol A epoxy resin in the bisphenol A epoxy resin emulsion with the medium molecular weight is as follows: 1000-1400.
The low-molecular-weight bisphenol A epoxy resin emulsion and the medium-molecular-weight bisphenol A epoxy resin emulsion are commercially available products.
Preferably, the lubricant comprises a lubricant A and a lubricant B, wherein the lubricant A is one of imidazoline cationic lubricant and a compound of imidazoline cationic lubricant and nonionic lubricant, and the lubricant B is organosilicon lubricant.
Preferably, the lubricant A is a compound of an imidazoline cationic lubricant and a nonionic lubricant, the mass ratio of the imidazoline cationic lubricant to the nonionic lubricant is 1:1.5-1:3.5, more preferably 1:2.1, and the nonionic lubricant is preferably polyoxyethylene ether. Imidazoline cationic and nonionic lubricants are commercially available products. The imidazoline cationic lubricant can effectively reduce the wool yarn phenomenon and improve the product quality; the compound of imidazoline cationic lubrication and nonionic lubricant has excellent lubricating performance, and can be widely used for processing various glass fibers of direct yarns, winding yarns, chopped yarns and jet yarns; the organosilicon lubricant can improve the strength of the glass fiber and has a coupling effect. The compound of the imidazoline cationic lubricant and the nonionic lubricant and the organic silicon lubricant are mixed for use, the effect is better than that of the lubricant which is singly used, and the hairiness is very little while the strength of the glass fiber is improved.
Preferably, the mass percentage of each component in the impregnating compound is as follows: 6-10% of film forming agent, 0.1-0.5% of lubricant A, 0.3-0.9% of lubricant B, 0.4-1.2% of coupling agent, 0.04-0.06% of pH regulator and the balance of deionized water.
Preferably, the mass fraction ratio of the low molecular weight bisphenol A epoxy resin emulsion to the medium molecular weight bisphenol A epoxy resin emulsion is 1:1-1.8:1, more preferably 1:1. The yarn produced by the impregnating compound prepared by adopting the synergistic effect of the bisphenol A epoxy resin emulsion with low molecular weight and the bisphenol A epoxy resin emulsion with medium molecular weight has good bundling property, less broken hairiness and good compatibility with a matrix material.
Preferably, the coupling agent is a silane coupling agent, and the silane coupling agent is one or two of a silane coupling agent KH570 and a silane coupling agent OFS-6032. As a preferable technical scheme, the coupling agent is preferably silane coupling agent OFS-6032, and the silane coupling agent OFS-6032 can be combined with a plurality of thermoplastic resins, has good resin wettability and can improve the bending strength and the tensile strength. As another preferable technical scheme, the coupling agent is preferably a mixture of a silane coupling agent KH570 and a silane coupling agent OFS-6032, and the two coupling agents are combined to prepare the impregnating compound, so that the mechanical property of the composite material produced by the yarns and the base material which are made of the impregnating compound can be improved.
The preparation method of the impregnating compound for the direct roving of the low-dielectric glass fiber comprises the following steps:
(1) adjusting the pH value of deionized water by using a pH regulator, adding a coupling agent, stirring, and standing to obtain a hydrolyzed coupling agent;
(2) diluting the lubricant B, the lubricant A and the film forming agent by deionized water respectively, and uniformly stirring to obtain a lubricant B diluent, a lubricant A diluent and a film forming agent diluent;
(3) and (3) adding deionized water into the container, adding the hydrolyzed coupling agent, uniformly stirring, sequentially adding the lubricant B diluent, the lubricant A diluent and the film-forming agent diluent obtained in the step (2), and finally adding deionized water and uniformly stirring to obtain the impregnating compound.
Preferably, the stirring speed in the step (1) is 60-80rpm, the stirring time is more than 30 minutes, the solution is clear, no oil on the surface is left, the hydrolysis is finished, then the solution is kept stand for 1-4 hours, and the environmental temperature of the standing is 0-10 ℃; the pH value range in the step (1) is 3-4, and the pH regulator is one of glacial acetic acid, citric acid and oxalic acid.
Preferably, step (2) is: mixing deionized water and the lubricant B according to the mass ratio of 1:1-2:1, and stirring for 10-20 minutes at the rotating speed of 58-62rmp to obtain a diluent of the lubricant B; mixing deionized water and the lubricant A according to the mass ratio of 5:1-20:1, and stirring for 5-10 minutes at the rotating speed of 58-62rmp to obtain a lubricant A diluent; mixing deionized water and the film-forming agent according to the mass ratio of 1:1-1.2:1, and stirring for 10-20 minutes at the rotating speed of 58-62rmp to obtain the film-forming agent diluent.
Preferably, the mass of the deionized water added into the container in the step (3) is 40-50% of the total mass of the impregnating compound, the stirring time in the step (3) is 10-20 minutes, and the stirring speed is 60-80 rmp.
In summary, the invention has the following advantages:
(1) the invention can reduce the hairiness of the direct low-dielectric glass fiber yarn, the hairiness is an important quality index which influences the appearance and the style of the yarn, the state of the hairiness of the yarn directly influences the weaving efficiency, the cloth cover style and the dyeing effect, the glass fiber yarn prepared by the treating compound has less hairiness, is not easy to generate hair grinding in the weaving process, can improve the quality of the yarn, improve the bundling property of the yarn, increase the flexibility of the yarn, improve the tensile strength and the bending strength of the yarn, and enhance the interface bonding force with resin.
(2) The invention adopts the film-forming agent mixed by the bisphenol A epoxy resin emulsion with low molecular weight and medium molecular weight to improve the bundling property of the low dielectric glass fiber direct yarn, so that the yarn body is compact, hairiness is reduced, and the compatibility with a matrix material is good, thereby the strength of the yarn is increased, and the flexibility of the yarn is better.
(3) According to the invention, the silane coupling agent OFS-6032 is added into the impregnating compound, so that the prepared yarn can be combined with a plurality of thermoplastic resins, the wetting property of the resins is good, the bending resistance and the tensile strength can be improved, the coupling agent is a mixture of the silane coupling agent KH570 and the silane coupling agent OFS-6032, and the mechanical property of the composite material can be improved by combining the two coupling agents.
(4) The compound of the imidazoline cationic lubricant and the nonionic lubricant is added into the sizing agent, so that the effect is better, the prepared yarn has less hairiness, the organosilicon lubricant can improve the strength of the glass fiber, and the organic silicon lubricating agent has a coupling effect. The compound of the imidazoline cationic lubricant and the nonionic lubricant is mixed with the organic silicon lubricant, so that the synergistic effect is good, the prepared yarn has better quality and less hairiness.
(5) The sizing agent prepared from the film forming agent, the organic silicon lubricant and the coupling agent can improve the bending resistance and the tensile strength of yarns and enhance the interface bonding force with matrix resin.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A sizing agent for direct roving of low-dielectric glass fibers comprises the following components in percentage by mass: 10% of film forming agent, 0.3% of lubricant A, 0.8% of organic silicon lubricant, 0.05% of silane coupling agent OFS-60320.6%, 0.05% of glacial acetic acid and the balance of deionized water. The film-forming agent is composed of a low-molecular-weight bisphenol A epoxy resin emulsion with the average molecular weight of 420 and a medium-molecular-weight bisphenol A epoxy resin emulsion with the average molecular weight of 1200, wherein the mass ratio of the low-molecular-weight bisphenol A epoxy resin emulsion to the medium-molecular-weight bisphenol A epoxy resin emulsion is 1:1. The lubricant A is obtained by compounding imidazoline cationic lubricant and polyoxyethylene ether according to the mass ratio of 1: 2.1.
A preparation method of a sizing agent for direct roving of low-dielectric glass fibers comprises the following steps:
(1) adjusting the pH value of deionized water to 4 by using glacial acetic acid, adding a silane coupling agent OFS-6032, stirring at the stirring speed of 60rmp for 30 minutes, and standing at 0 ℃ for 4 hours to obtain a hydrolyzed silane coupling agent OFS-6032;
(2) mixing an organic silicon lubricant and deionized water according to the mass ratio of 1:1.5, and stirring for 15 minutes at the rotating speed of 60rmp to obtain an organic silicon lubricant diluent; stirring deionized water and a lubricant A at a mass ratio of 20:1 at a rotating speed of 60rmp for 5 minutes to obtain a lubricant A diluent; mixing deionized water and a film-forming agent according to a mass ratio of 1:1, and stirring for 15 minutes at a rotating speed of 60rmp to obtain a film-forming agent diluent;
(3) and (2) adding deionized water accounting for 40% of the total mass of the impregnating compound into a preparation kettle, adding the silane coupling agent OFS-6032 hydrolyzed in the step (1), stirring for 10 minutes at the rotating speed of 80rmp, sequentially adding the organic silicon lubricant diluent, the lubricant A diluent and the film forming agent diluent obtained in the step (2), finally adding deionized water, and stirring for 20 minutes at the rotating speed of 80rmp to obtain the impregnating compound.
Example 2
A sizing agent for direct roving of low-dielectric glass fibers comprises the following components in percentage by mass: 6% of film forming agent, 0.25% of imidazoline cationic lubricant, 0.6% of organic silicon lubricant, 0.6% of silane coupling agent, 0.04% of citric acid and the balance of deionized water. Wherein the film-forming agent consists of a low-molecular-weight bisphenol A epoxy resin emulsion with the average molecular weight of 430 and a medium-molecular-weight bisphenol A epoxy resin emulsion with the average molecular weight of 1400, wherein the mass ratio of the low-molecular-weight bisphenol A epoxy resin emulsion to the medium-molecular-weight bisphenol A epoxy resin emulsion is 1.8: 1; the silane coupling agent is prepared by mixing a silane coupling agent KH570 and a silane coupling agent OFS-6032 according to the mass ratio of 1:1.
A preparation method of a sizing agent for direct roving of low-dielectric glass fibers comprises the following steps:
(1) adjusting the pH value of deionized water to 3 by using citric acid, adding a silane coupling agent, stirring at the stirring speed of 80rmp for 40 minutes, clarifying the solution until no oil stains exist on the surface, namely, finishing hydrolysis, and standing at 10 ℃ for 3 hours to obtain the hydrolyzed silane coupling agent;
(2) mixing deionized water and an organic silicon lubricant according to a mass ratio of 2:1, and stirring for 20 minutes at a rotating speed of 62rmp to obtain an organic silicon lubricant diluent; mixing deionized water and the imidazoline cationic lubricant according to the mass ratio of 10:1, and stirring for 10 minutes at the rotating speed of 60rmp to obtain an imidazoline cationic lubricant diluent; mixing a film forming agent and deionized water according to a mass ratio of 1:1, and stirring for 20 minutes at a rotating speed of 60rmp to obtain a film forming agent diluent;
(3) and (2) adding deionized water accounting for 50% of the total mass of the impregnating compound into a preparation kettle, adding the silane coupling agent hydrolyzed in the step (1), stirring at the rotating speed of 70rmp for 20 minutes, sequentially adding the organic silicon lubricant diluent, the imidazoline cationic lubricant diluent and the film forming agent diluent obtained in the step (2), finally adding deionized water, and stirring at the rotating speed of 70rmp for 15 minutes to obtain the impregnating compound.
Example 3
A sizing agent for direct roving of low-dielectric glass fibers comprises the following components in percentage by mass: 6% of film forming agent, 0.25% of polyoxyethylene ether, 0.6% of organic silicon lubricant, 0.06% of silane coupling agent KH 5700.6%, 0.06% of oxalic acid and the balance of deionized water.
The film-forming agent is composed of a low-molecular-weight bisphenol A epoxy resin emulsion with the average molecular weight of 410 and a medium-molecular-weight bisphenol A epoxy resin emulsion with the average molecular weight of 1100, wherein the mass ratio of the low-molecular-weight bisphenol A epoxy resin emulsion to the medium-molecular-weight bisphenol A epoxy resin emulsion is 1.5: 1.
A preparation method of a sizing agent for direct roving of low-dielectric glass fibers comprises the following steps:
(1) adjusting the pH value of deionized water to 3.5 by oxalic acid, adding a coupling agent, stirring at the stirring speed of 70rmp for 50 minutes, and standing at 5 ℃ for 1 hour to obtain a hydrolyzed silane coupling agent KH 570;
(2) mixing an organic silicon lubricant and deionized water according to the mass ratio of 1:1, and stirring for 10 minutes at the rotating speed of 60rmp to obtain an organic silicon lubricant diluent; mixing deionized water and polyoxyethylene ether according to the mass ratio of 5:1, and stirring for 8 minutes at the rotating speed of 60rmp to obtain polyoxyethylene ether diluent; mixing deionized water and a film-forming agent according to a mass ratio of 1:1, and stirring for 10 minutes at a rotating speed of 60rmp to obtain a film-forming agent diluent;
(3) and (3) adding deionized water accounting for 40% of the total mass of the impregnating compound into the preparation kettle, adding the hydrolyzed silane coupling agent KH570, stirring for 10 minutes at the rotating speed of 70rmp, sequentially adding the organic silicon lubricant diluent, the polyoxyethylene ether diluent and the film-forming agent diluent obtained in the step (2), finally adding deionized water, and stirring for 10 minutes at the rotating speed of 70rmp to obtain the impregnating compound.
Comparative example 1
The comparative example is substantially the same as the technical scheme of the example 1, except that: the film former consists only of a low molecular weight bisphenol a type epoxy resin emulsion having an average molecular weight of 420.
Comparative example 2
The comparative example is substantially the same as the technical scheme of the example 1, except that: the film former consists only of a medium molecular weight bisphenol a type epoxy resin emulsion having an average molecular weight of 1200.
The impregnating compounds prepared in the above examples and comparative examples were used to produce low dielectric glass fiber yarns according to the conventional low dielectric glass fiber production process in the art, and the produced low dielectric glass fiber yarns were subjected to the following tests.
Indexes such as hairiness, breaking strength and the like of each group of yarns are respectively tested by using a YG172A type yarn hairiness tester and a YG063 single yarn strength tester. The test conditions were 62% relative humidity, 24 ℃ temperature and the experimental data are shown in table 1.
TABLE 1 comparison of various test indexes of yarn
In Table 1, "O" represents that the yarn used has good bundling property, and "X" represents that the yarn has poor bundling property. As can be seen from the data in Table 1, the hairiness index of the yarn made by the treating compound is obviously lower than that of the yarn made by the treating compound of the comparative example, and the yarn made by the treating compound of the invention has good convergence and high breaking strength, so the yarn has smooth surface, soft hand feeling and good elasticity and extensibility. Example 1 the use of a combination of imidazoline cationic lubricant and nonionic lubricant is more effective and minimizes hairiness than either lubricant alone.
The glass fiber and the polypropylene resin prepared by the impregnating compounds of the examples 1 to 3 and the comparative example 1 are respectively made into resin glass fiber composite materials by the prior art commonly used in the field, and the tensile property, the bending property and the compatibility with the matrix resin of the four resin glass fiber composite materials are respectively tested, and the test results are shown in table 2:
TABLE 2 Performance testing of resin glass fiber composites
| Group of | Compatibility with matrix resins | Flexural Strength/MPa | Tensile strength/MPa |
| Example 1 | O | 163.1 | 94.55 |
| Example 2 | O | 158.3 | 91.03 |
| Example 3 | O | 159.7 | 91.98 |
| Comparative example 1 | X | 143.6 | 84.98 |
In table 2, "O" represents that the compatibility of the yarn with the matrix resin material is good, and "X" represents that the compatibility of the yarn with the matrix resin material is not good. As can be seen from the data in Table 2, the tensile strength and the bending strength of the resin glass fiber composite material synthesized by the yarns prepared by using the sizing agent prepared by the invention reach 163.1MPa and 94.55MPa, the yarns prepared by using the sizing agents provided in examples 1 to 3 have good compatibility with the matrix resin material, and also have good tensile strength and bending strength, which indicates that the yarns prepared by using the sizing agent provided by the invention have stronger interfacial bonding force with the resin.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The impregnating compound for the direct roving of the low-dielectric glass fiber is characterized by comprising the following components: the coating comprises a film forming agent, a lubricant, a coupling agent, a pH regulator and deionized water, wherein the film forming agent is composed of a low-molecular-weight bisphenol A epoxy resin emulsion and a medium-molecular-weight bisphenol A epoxy resin emulsion, and the molecular weight range of bisphenol A epoxy resin in the low-molecular-weight bisphenol A epoxy resin emulsion is as follows: 300-450, the molecular weight range of the bisphenol A epoxy resin in the bisphenol A epoxy resin emulsion with the medium molecular weight is as follows: 1000-1400.
2. The sizing agent for the direct roving of the low dielectric glass fiber as claimed in claim 1, wherein: the lubricant comprises a lubricant A and a lubricant B, wherein the lubricant A is one of imidazoline cationic lubricant and a compound of imidazoline cationic lubricant and nonionic lubricant, and the lubricant B is organic silicon lubricant.
3. The sizing agent for the direct roving of the low dielectric glass fiber as claimed in claim 2, wherein: the lubricant A is a compound of an imidazoline cationic lubricant and a nonionic lubricant, and the mass ratio of the imidazoline cationic lubricant to the nonionic lubricant is 1:1.5-1: 3.5.
4. The impregnating compound for the direct roving of the low-dielectric glass fiber as claimed in claim 2, wherein the mass percentage of each component in the impregnating compound is as follows: 6-10% of film forming agent, 0.1-0.5% of lubricant A, 0.3-0.9% of lubricant B, 0.4-1.2% of coupling agent, 0.04-0.06% of pH regulator and the balance of deionized water.
5. The sizing agent for the direct roving of the low dielectric glass fiber as claimed in claim 1, wherein: the mass ratio of the low-molecular-weight bisphenol A epoxy resin emulsion to the medium-molecular-weight bisphenol A epoxy resin emulsion is 1:1-1.8: 1.
6. A sizing agent for direct roving of low dielectric glass fibers according to any one of claims 1 to 5, wherein: the coupling agent is a silane coupling agent, and the silane coupling agent is one or two of a silane coupling agent KH570 and a silane coupling agent OFS-6032.
7. A method for preparing the impregnating compound for the direct roving of the low dielectric glass fiber as claimed in any one of claims 2 to 4, which comprises the following steps:
(1) adjusting the pH value of deionized water by using a pH regulator, adding a coupling agent, stirring, and standing to obtain a hydrolyzed coupling agent;
(2) diluting the lubricant B, the lubricant A and the film forming agent by deionized water respectively, and uniformly stirring to obtain a lubricant B diluent, a lubricant A diluent and a film forming agent diluent;
(3) and (3) adding deionized water into the container, adding the hydrolyzed coupling agent, uniformly stirring, sequentially adding the lubricant B diluent, the lubricant A diluent and the film-forming agent diluent obtained in the step (2), and finally adding deionized water and uniformly stirring to obtain the impregnating compound.
8. The method for preparing the impregnating compound for the direct roving of the low-dielectric glass fiber as claimed in claim 7, wherein: in the step (1), the stirring speed is 60-80rpm, the stirring time is more than 30 minutes, the standing time is 1-4 hours, and the standing ambient temperature is 0-10 ℃; the pH value range in the step (1) is 3-4, and the pH regulator is one of glacial acetic acid, citric acid and oxalic acid.
9. The method for preparing the impregnating compound for the direct roving of the low-dielectric glass fiber according to claim 7, wherein the step (2) is: mixing deionized water and the lubricant B according to the mass ratio of 1:1-2:1, and stirring for 10-20 minutes at the rotating speed of 58-62rmp to obtain a diluent of the lubricant B; mixing deionized water and the lubricant A according to the mass ratio of 5:1-20:1, and stirring for 5-10 minutes at the rotating speed of 58-62rmp to obtain a lubricant A diluent; mixing deionized water and the film-forming agent according to the mass ratio of 1:1-1.2:1, and stirring for 10-20 minutes at the rotating speed of 58-62rmp to obtain the film-forming agent diluent.
10. The method for preparing the impregnating compound for the direct roving of the low-dielectric glass fiber as claimed in claim 7, wherein: in the step (3), deionized water is added into the container, the mass of the deionized water accounts for 40-50% of the total mass of the impregnating compound, the stirring time in the step (3) is 10-20 minutes, and the stirring speed is 60-80 rmp.
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