CN116535111B - Impregnating compound for low-twist electronic grade glass fiber, preparation method and application thereof - Google Patents
Impregnating compound for low-twist electronic grade glass fiber, preparation method and application thereof Download PDFInfo
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- CN116535111B CN116535111B CN202310086671.3A CN202310086671A CN116535111B CN 116535111 B CN116535111 B CN 116535111B CN 202310086671 A CN202310086671 A CN 202310086671A CN 116535111 B CN116535111 B CN 116535111B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 94
- 239000003365 glass fiber Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 78
- 229920001685 Amylomaize Polymers 0.000 claims abstract description 53
- 229920000945 Amylopectin Polymers 0.000 claims abstract description 48
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000004513 sizing Methods 0.000 claims abstract description 46
- 239000007787 solid Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004519 grease Substances 0.000 claims abstract description 36
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 31
- 239000000314 lubricant Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- 229920002472 Starch Polymers 0.000 claims description 34
- 235000019698 starch Nutrition 0.000 claims description 34
- 239000008107 starch Substances 0.000 claims description 33
- 239000004014 plasticizer Substances 0.000 claims description 30
- 239000000839 emulsion Substances 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 229920000856 Amylose Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000006467 substitution reaction Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 13
- 239000013530 defoamer Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- 244000068988 Glycine max Species 0.000 claims description 9
- 235000010469 Glycine max Nutrition 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 229920002261 Corn starch Polymers 0.000 claims description 8
- 239000008120 corn starch Substances 0.000 claims description 8
- 240000003183 Manihot esculenta Species 0.000 claims description 7
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 7
- 238000010411 cooking Methods 0.000 claims description 7
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 3
- 244000105624 Arachis hypogaea Species 0.000 claims description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 3
- 235000018262 Arachis monticola Nutrition 0.000 claims description 3
- 235000004443 Ricinus communis Nutrition 0.000 claims description 3
- 235000020232 peanut Nutrition 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000004744 fabric Substances 0.000 description 19
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 206010020112 Hirsutism Diseases 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000009941 weaving Methods 0.000 description 8
- 230000035699 permeability Effects 0.000 description 7
- 238000010025 steaming Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 239000010512 hydrogenated peanut oil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- ZRJOUVOXPWNFOF-UHFFFAOYSA-N 3-dodecoxypropan-1-amine Chemical compound CCCCCCCCCCCCOCCCN ZRJOUVOXPWNFOF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MMWFTWUMBYZIRZ-UHFFFAOYSA-N n,n-dimethylundecan-1-amine Chemical compound CCCCCCCCCCCN(C)C MMWFTWUMBYZIRZ-UHFFFAOYSA-N 0.000 description 1
- OMEMQVZNTDHENJ-UHFFFAOYSA-N n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCNC OMEMQVZNTDHENJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000009423 ventilation Methods 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
- C03C25/007—Impregnation by solution; Solution doping or molecular stuffing of porous glass
-
- 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
- C03C25/12—General methods of coating; Devices therefor
- C03C25/16—Dipping
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The application provides a sizing agent for low-twist electronic grade glass fibers, which comprises an effective component and water, wherein the solid content of the sizing agent is 6.144-13.615%, and the effective component comprises a main film forming agent, grease, an emulsifying agent, a plasticizing agent, a defoaming agent, a lubricating agent and ammonia water; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows: 5.0 to 10.0 percent of main film forming agent, 0.8 to 2.0 percent of grease, 0.04 to 0.1 percent of emulsifying agent, 0.1 to 1.0 percent of plasticizing agent and 0.2 to 0.5 percent of lubricating agent; 0.001 to 0.005 percent of defoaming agent; 0.003 to 0.010 percent of ammonia water; the main film forming agent is a mixture of high-amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high-amylose starch to the hydroxyethyl modified amylopectin is 1: 2-3: 2. the impregnating compound is suitable for the production of low-twist electronic grade glass fibers, and can effectively solve the problems of Mao Yugao, poor wear resistance and poor bundling property caused by low twist in the production process of the low-twist electronic grade glass fibers.
Description
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 especially relates to a low-twist impregnating compound for electronic-grade glass fibers, and a preparation method and application thereof.
Background
The electronic grade glass fiber cloth is an inorganic nonmetallic material for producing copper-clad plates and printed circuit boards, and has the characteristics of good electrical insulation performance, fire resistance, flame retardance, water resistance, aging resistance, weather resistance, high strength, high modulus and the like. The diameter of the single fiber of the electronic grade glass fiber yarn for weaving is 9 mu m or less, and a plurality of monofilaments are clustered into one yarn, which is brittle, has poor wear resistance and poor bundling property, so that a layer of impregnating compound is coated on the surface of the yarn in the wire drawing process of the electronic grade glass fiber production process to change the surface characteristics of the original bare fiber and has the functions of lubricating and protecting the yarn.
The requirements of the current industry on the surface defect point condition, the dimensional stability, the thickness, the surface air permeability and the like of electronic grade glass fiber cloth products in copper-clad plates and printed circuit boards are higher and higher. The common practice in industry is to improve the bundling property of yarns through high twist so that the yarns are not easy to loosen in the weaving process, thereby reducing the generation of cloth cover defects. And then carrying out high-pressure fiber opening on the produced grey cloth to open the twist of the yarn, so that the warp and weft yarns of the cloth cover are dispersed, and the thickness and air permeability of the cloth cover are reduced. However, the cloth cover is opened in a high-pressure fiber opening mode, so that the problems of yarn breakage, weft inclination and the like of the cloth cover can occur, adverse effects can be brought to subsequent use, such as poor infiltration and size deviation can occur during downstream rubberizing, and the use effect is poor. There is a limit to the way high pressure fiber opening is used.
The cloth cover woven by the low-twist yarn does not need to be opened by high pressure, low ventilation and flat cloth cover can be obtained by spraying under normal pressure or low pressure, the damage to the cloth cover can not be increased, and the method has the advantages in the aspects of improving the production efficiency and reducing the energy sources. However, the low twist electronic yarn has the disadvantages of poor wear resistance, more hairiness, poor bundling property, poor weaving property and the like, and thus, the high requirement is put on the sizing agent used as the surface treating agent.
Disclosure of Invention
The purpose of the application is to solve the problems, and provide the impregnating compound for the low-twist electronic grade glass fiber, which has strong yarn coating capability and interface bonding capability with yarns, so that the bundling property and the wear resistance of the yarns are improved, and the problems of high hairiness, poor wear resistance, poor bundling property, poor weaving property and the like of the low-twist electronic grade glass fiber yarns in the production process can be solved; the electronic grade glass fiber yarn produced by coating the sizing agent has excellent weaving performance, is not easy to generate defects, and can obtain electronic cloth products with low air permeability, high dimensional stability and flat cloth cover, which meet the subsequent processing requirements, by adopting normal pressure or low pressure spraying.
According to one aspect of the application, there is provided a sizing agent for low twist electronic grade glass fibers, the sizing agent comprising an effective component and water, the sizing agent having a solids content of 6.144-13.615%, the effective component comprising a primary film former, grease, an emulsifier, a plasticizer, a lubricant, a defoamer and aqueous ammonia; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the main film forming agent is a mixture of high-amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high-amylose starch to the hydroxyethyl modified amylopectin is 1: 2-3: 2.
wherein the solid content of the impregnating compound is 7.555-11.115%, and the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the main film forming agent is a mixture of high-amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high-amylose starch to the hydroxyethyl modified amylopectin is 1.5:2 to 2.5:2.
wherein the high amylose starch comprises high amylose tapioca starch or/and high amylose corn starch, and the linear content of the high amylose starch is 50-70%; the substitution degree of the hydroxyethyl modified amylopectin is 0.02-0.20%.
Wherein the grease is at least one of hydrogenated modified soybean phosphate grease, hydrogenated castor grease and hydrogenated peanut grease; the plasticizer is at least one of glycerol, polyethylene glycol, dioctyl terephthalate and dioctyl phthalate.
Wherein the emulsifier is at least one of polyoxyethylene ether, polyurethane and higher alkylamine.
Wherein the lubricant is at least one of methyl octadecabonate, polyethylene polyamine and ester quaternary ammonium salt; the defoamer is polyether modified organic silicon quaternary amine salt defoamer.
Wherein the solid content of the impregnating compound is 8.355-10.395%, and the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the main film forming agent is a mixture of high-amylose starch and hydroxyethyl modified amylopectin, the linear chain content of the high-amylose starch is 55-65%, and the substitution degree of the hydroxyethyl modified amylopectin is 0.05-0.10%; the grease is hydrogenated modified soybean phosphate grease; the mass ratio of the emulsifier to the polyoxyethylene ether to the polyurethane is 1: 2-2: 1, a mixture of two or more of the above-mentioned materials; the mass ratio of the polyethylene glycol to the dioctyl terephthalate serving as the plasticizer is 1: 2-3: 1, a mixture of two or more of the above-mentioned materials; the lubricant is ester quaternary ammonium salt; the defoaming agent is an organosilicon quaternary ammonium salt defoaming agent.
The primary film former of the present application is a mixture of high amylose starch and hydroxyethyl modified amylopectin. The high amylose starch has excellent film forming performance, and the formed film has high strength and enough toughness, but has low self gelatinization degree, is easy to regenerate, and the prepared impregnating compound is easy to be layered and invalid; the hydroxyethyl modified amylopectin has poor film forming effect, but has high gelatinization degree, and can improve the hydrophilicity and stability of the film, thereby reducing the retrogradation phenomenon of starch slurry and improving the binding capacity of the impregnating compound. The two starches are matched for use, so that the defect that the starch type impregnating compound is easy to delaminate can be overcome, the gelatinization degree of the starch is improved, and the coating effect of the impregnating compound is further improved. In addition, the percentage of the solid mass of the main film forming agent in the total mass of the impregnating compound needs to be controlled in a certain range, if the using amount is too large, the viscosity of the impregnating compound is too high, the use ratio of the impregnating compound is low, most of the impregnating compound is wasted, yarn powder falling in the weaving process is increased, and the main nozzle and the auxiliary nozzle are easily blocked, so that rough yarn is produced; too small an amount may result in a decrease in the coating performance of the sizing agent, a decrease in the bundling property of the yarn, and an increase in hairiness. Therefore, the solid mass of the main film forming agent is controlled to be 5.0-10.0%, preferably 6.0-8.0%, and more preferably 6.3-7.3% of the total mass of the impregnating compound.
Meanwhile, the mass ratio of high amylose starch and hydroxyethyl modified amylopectin in the main film forming agent is controlled, so that the use effect of the sizing agent is further improved. Preferably, the present application controls the mass ratio of high amylose starch and hydroxyethyl modified amylopectin to be 1: 2-3: 2; more preferably, the mass ratio of high amylose starch to hydroxyethyl modified amylopectin is 1.5:2 to 2.5:2. if the consumption of high amylose is excessive, the solubility of starch in water can be reduced, and the impregnating compound is more easy to regenerate and lose efficacy; if the amount of hydroxyethyl modified amylopectin is too large, the film-forming effect is poor and the oiling effect is poor.
In addition, high amylose starches as used herein include high amylose tapioca starch and/or high amylose corn starch. The linear chain content of the high amylose starch is controlled to be 50-70%, preferably 55-65%; when the linear chain content is too high, the starch has low self-gelatinization degree, is easy to regenerate, and the prepared impregnating compound is easy to be layered and invalid; when the linear chain content is too low, the formed film has low strength and insufficient toughness. The substitution degree of the hydroxyethyl modified amylopectin is controlled to be 0.02-0.20%, preferably 0.05-0.10%; when the substitution degree is too high, the film forming effect is poor; when the substitution degree is too low, the binding capacity of the sizing agent and the yarns is reduced, so that the powder falling is increased.
The grease is used for increasing the compatibility degree of starch and water, increasing the toughness of film formation and simultaneously playing a role in lubrication. The fat used in the present application is at least one of hydrogenated soybean phosphate fat, hydrogenated castor fat and hydrogenated peanut fat, which have high compatibility with starch and low melting point. Meanwhile, the grease amount needs to be matched with the starch amount for use, the phenomenon of increased powder falling occurs when the use amount is small, and the filament is formed poorly when the use amount is large. Therefore, the percentage of the solid mass of the control grease in the total mass of the impregnating compound is 0.8-2.0%, preferably 1.0-1.8%, and more preferably 1.5-1.8%.
The use of the plasticizer can improve the strength and toughness of the starch film and play a role in softening the sizing agent film. The softened impregnating compound film can be better combined with the surface of the glass fiber yarn, so that the wear resistance and the bundling property of the yarn are improved. The combination of the plasticizer, starch and grease is an important point in the application. In the present application, the plasticizer used is preferably at least one of glycerol, polyethylene glycol, dioctyl terephthalate and dioctyl phthalate. Because the plasticizing effect of different plasticizers is different, through a large amount of experiments, the application shows that the combination of two or more plasticizers can increase the strength and toughness of the sizing agent film and improve the bonding degree of the sizing agent and the glass fiber yarns. More preferably, the plasticizer is a mixture of polyethylene glycol and dioctyl terephthalate in a mass ratio of 1:2-3:1. Meanwhile, the addition amount of the plasticizer is combined with the use amount of the starch and the grease; too little plasticizer is added to play a role in softening the sizing agent film, so that the wear resistance of the yarn is poor and hairiness is increased; if the amount is too large, the strength of the film is lowered, the film is broken, and the effect of coating the glass fiber yarn cannot be achieved. In the present application, the solid mass of the plasticizer is controlled to be 0.1 to 1.0% by weight, preferably 0.2 to 0.8% by weight, based on the total mass of the sizing agent.
The emulsifier is mainly used for emulsifying the hydrogenated oil, and the use of the emulsifier can improve the compatibility of starch, water and oil and improve the emulsifying effect. The emulsifier used in the application is at least one of polyoxyethylene ether, polyurethane and higher alkylamine; preferably, the emulsifier is at least one of polyoxyethylene ether, polyurethane, N-dodecylmethylamine, 3-dodecyloxypropylamine and N, N-undecyldimethylamine. Since the oils are generally mixtures, it is correspondingly necessary to select at least one emulsifier for mixing in order to better emulsify the oils. Therefore, the emulsifier is preferably a mixture of polyoxyethylene ether and polyurethane in a mass ratio of 1:2 to 2:1. 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; and excessive usage can affect the oiling condition of the impregnating compound. The solid mass of the emulsifier is controlled to be 0.04-0.1%, preferably 0.05-0.1%, more preferably 0.05-0.08% of the total mass of the impregnating compound.
The lubricant can play a role of smoothing the yarn, so that hairiness and yarn broken phenomena generated by friction in the production process of the yarn are reduced. In the present application, the lubricant is at least one of methyl octadecabonate, polyethylene polyamine and ester-based quaternary ammonium salt. The use of grease alone is not sufficient to increase the degree of lubrication of the sizing agent and it is desirable to increase the amount of lubricant suitable for starch systems. Meanwhile, the dosage of the lubricant needs to be controlled in a proper range; the lubricant is excessively used, slipping occurs in the wire drawing process, and the forming of the precursor wire is poor; too little amount of lubricant will result in poor yarn lubricity and increased likelihood of hairiness and yarn breakage. Thus, the control lubricant herein has a solids mass of 0.2 to 0.5%, preferably 0.3 to 0.4% by weight of the total mass of the sizing agent.
The use of the defoamer can reduce the condition of more foam of the impregnating compound. In the application, the defoamer is polyether modified organic silicon quaternary amine salt defoamer. The adding amount of the defoaming agent is not required to be too large, waste is caused by too large adding amount, and the required effect cannot be achieved by too small adding amount. Thus, the solid mass of the defoamer is controlled to be 0.001 to 0.005%, preferably 0.002 to 0.005% of the total mass of the sizing agent.
In the application, the ammonia water is used for adjusting the pH value of the impregnating compound, controlling the pH value of the impregnating compound to be neutral or weak acidity, and improving the stability of the impregnating compound. The solid mass of the ammonia water is controlled to be 0.003-0.010% of the total mass of the impregnating compound.
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 remaining portion of the emulsion after drying under certain conditions to remove water. The sizing agent for low-twist electronic grade glass fibers of the present application has a solid content of 6.144 to 13.615%, preferably 7.555 to 11.115%, and more preferably 8.355 to 10.395%.
According to a second aspect of the present application, there is provided a method for preparing the sizing agent for low twist electronic grade glass fiber, comprising the steps of:
adding the main film forming agent into normal-temperature water which is 5-10 times of the main film forming agent, stirring and dispersing, then passing through a high-temperature high-pressure digester, and after the high-temperature high-pressure digester is heated to a first preset temperature and is pressurized to a first preset pressure, cooking at a first preset cooking flow, adding warm water accounting for 20-30% of the total mass of the sizing agent after cooking is finished, and cooling to obtain starch slurry;
adding the emulsifier and the grease into water with the mass which is 5-8 times of that of the second preset temperature, stirring for a first preset time at a first rotating speed, adding the plasticizer, and stirring to obtain a first emulsion;
adding the lubricant into water with the mass which is 10-20 times of that of the third preset temperature, and stirring to obtain a second emulsion;
adding the first emulsion and the second emulsion into the starch slurry, supplementing the residual water, and then adding the defoaming agent and the ammonia water to obtain an initial impregnating compound;
homogenizing the initial impregnating compound under a second preset pressure by a homogenizer to reach qualified particle size, and obtaining the impregnating compound.
It should be noted that the three steps of preparing starch slurry, first emulsion and second emulsion are not sequential and can be adjusted according to the actual conditions of production.
Wherein the first preset temperature is 100-140 ℃; preferably, the temperature is 110-130 ℃;
wherein the first preset pressure is 1-7 kgf/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, it is 2 to 5kgf/cm 2 。
Wherein the first preset cooking flow is 500-2000L/h; preferably 800-1500L/h.
Wherein the second preset temperature is 50-80 ℃; preferably, it is 60 to 75 ℃.
Wherein the first rotating speed is 800-5000 rpm/min; preferably, it is 1000 to 4000rpm/min.
Wherein the first preset time period is 10-80 min; preferably, it is 30 to 60 minutes.
Wherein the third preset temperature is 40-80 ℃; preferably, it is 50 to 60 ℃.
Wherein the second preset pressure is 80-250 kgf/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, it is 100 to 200kgf/cm 2 。
Wherein the acceptable particle size is less than or equal to 8 mu m; preferably, it is 5 μm or less.
The preparation mode of homogenizing the impregnating compound into small particle size through certain pressure is an important point of the application. The size of the impregnating compound can influence the dispersion degree of the impregnating compound on the precursor, in the application, the prepared impregnating compound is homogenized through the homogenizer under the specific pressure parameter of the application, the size of the impregnating compound is reduced, the obtained small-size impregnating compound is easier to coat on the surface layer of the precursor, the impregnating compound can be prevented from being thrown away in the production process, and the waste of the impregnating compound is increased. Therefore, the particle size of the sizing agent in the present application is preferably 5 μm or less.
According to a third aspect of the present application, there is provided a low twist electronic grade glass fiber product produced from the foregoing low twist electronic grade glass fiber coated with a sizing.
According to a fourth aspect of the present application, there is provided the use of the aforementioned low twist electronic grade glass fiber product in the field of manufacturing copper clad laminates and printed circuit boards.
According to the preparation method, the main film forming agent, the grease, the emulsifying agent, the plasticizer, the defoaming agent, the lubricating agent and the ammonia water are matched for use, and based on a large amount of experimental researches and production application, the formula is optimally designed to form the impregnating compound for the low-twist electronic-grade glass fiber, and the impregnating compound is high-temperature starch-type impregnating compound, so that the impregnating compound can be suitable for being prepared by adopting a high-temperature high-pressure digester. The impregnating compound is suitable for the production of low-twist electronic grade glass fibers, can solve the problems of Mao Yugao, poor wear resistance and poor beam collecting property caused by low twist of the glass fibers in the production process, has excellent weaving performance of electronic grade glass fiber electronic yarns produced by coating the impregnating compound, has few defects of cloth cover, is easy to desize and open, has low air permeability and thickness of finished cloth, has good resin bonding property, and can be widely applied to the fields of manufacturing copper-clad plates and printed circuit boards.
The beneficial effects of the selection of the components and the contents of the sizing agent for the low-twist electronic grade glass fiber are illustrated by specific experimental data given in examples.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. 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 following are examples of preferred ranges of values for the components included in the sizing for low twist electronic grade glass fibers according to the present application.
Preferred examples one
The impregnating compound for the low-twist electronic grade glass fiber comprises an effective component and water, wherein the solid content of the impregnating compound is 6.144-13.615%, and the effective component comprises a main film forming agent, grease, an emulsifying agent, a plasticizer, a lubricant, a defoaming agent and ammonia water; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the main film forming agent is the mixture of high amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high amylose starch to the hydroxyethyl modified amylopectin is 1: 2-3: 2.
preferred example two
The impregnating compound for the low-twist electronic grade glass fiber comprises an effective component and water, wherein the solid content of the impregnating compound is 7.555-11.115%, and the effective component comprises a main film forming agent, grease, an emulsifying agent, a plasticizer, a lubricant, a defoaming agent and ammonia water; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the main film forming agent is a mixture of high-amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high-amylose starch to the hydroxyethyl modified amylopectin is 1.5:2 to 2.5:2
Preferred examples three
The impregnating compound for the low-twist electronic grade glass fiber comprises an effective component and water, wherein the solid content of the impregnating compound is 6.144-13.615%, and the effective component comprises a main film forming agent, grease, an emulsifying agent, a plasticizer, a lubricant, a defoaming agent and ammonia water; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the main film forming agent is the mixture of high amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high amylose starch to the hydroxyethyl modified amylopectin is 1: 2-3: 2; the high amylose starch comprises high amylose tapioca starch or/and high amylose corn starch, and the linear content of the high amylose starch is 50-70%; the substitution degree of the hydroxyethyl modified amylopectin is 0.02-0.20%.
Preferred example four
The impregnating compound for the low-twist electronic grade glass fiber comprises an effective component and water, wherein the solid content of the impregnating compound is 6.144-13.615%, and the effective component comprises a main film forming agent, grease, an emulsifying agent, a plasticizer, a lubricant, a defoaming agent and ammonia water; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the main film forming agent is the mixture of high amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high amylose starch to the hydroxyethyl modified amylopectin is 1: 2-3: 2; the high amylose starch comprises high amylose tapioca starch or/and high amylose corn starch, and the linear content of the high amylose starch is 50-70%; the substitution degree of the hydroxyethyl modified amylopectin is 0.02-0.20%; the oil is at least one of hydrogenated modified soybean phosphate oil, hydrogenated castor oil and hydrogenated peanut oil; the plasticizer is at least one of glycerol, polyethylene glycol, dioctyl terephthalate and dioctyl phthalate.
Preferred example five
The impregnating compound for the low-twist electronic grade glass fiber comprises an effective component and water, wherein the solid content of the impregnating compound is 6.144-13.615%, and the effective component comprises a main film forming agent, grease, an emulsifying agent, a plasticizer, a lubricant, a defoaming agent and ammonia water; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the main film forming agent is the mixture of high amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high amylose starch to the hydroxyethyl modified amylopectin is 1: 2-3: 2; the high amylose starch comprises high amylose tapioca starch or/and high amylose corn starch, and the linear content of the high amylose starch is 50-70%; the substitution degree of the hydroxyethyl modified amylopectin is 0.02-0.20%; the oil is at least one of hydrogenated modified soybean phosphate oil, hydrogenated castor oil and hydrogenated peanut oil; the plasticizer is at least one of glycerol, polyethylene glycol, dioctyl terephthalate and dioctyl phthalate; the emulsifier is at least one of polyoxyethylene ether, polyurethane and higher alkylamine.
Preferred example six
The impregnating compound for the low-twist electronic grade glass fiber comprises an effective component and water, wherein the solid content of the impregnating compound is 6.144-13.615%, and the effective component comprises a main film forming agent, grease, an emulsifying agent, a plasticizer, a lubricant, a defoaming agent and ammonia water; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the main film forming agent is the mixture of high amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high amylose starch to the hydroxyethyl modified amylopectin is 1: 2-3: 2; the high amylose starch comprises high amylose tapioca starch or/and high amylose corn starch, and the linear content of the high amylose starch is 50-70%; the substitution degree of the hydroxyethyl modified amylopectin is 0.02-0.20%; the oil is at least one of hydrogenated modified soybean phosphate oil, hydrogenated castor oil and hydrogenated peanut oil; the plasticizer is at least one of glycerol, polyethylene glycol, dioctyl terephthalate and dioctyl phthalate; the emulsifier is at least one of polyoxyethylene ether, polyurethane and higher alkylamine; the lubricant is at least one of methyl octadecabonate, polyethylene polyamine and ester quaternary ammonium salt; the defoamer is polyether modified organic silicon quaternary amine salt defoamer.
Preferred examples seven
The impregnating compound for the low-twist electronic grade glass fiber comprises an effective component and water, wherein the solid content of the impregnating compound is 8.355-10.395%, and the effective component comprises a main film forming agent, grease, an emulsifying agent, a plasticizer, a lubricant, a defoaming agent and ammonia water; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the main film forming agent is the mixture of high amylose starch and hydroxyethyl modified amylopectin, the linear chain content of the high amylose starch is 55-65%, and the substitution degree of the hydroxyethyl modified amylopectin is 0.05-0.10%; the oil is hydrogenated modified soybean phosphate oil; the emulsifier is a mixture of polyoxyethylene ether and polyurethane with the mass ratio of 1:2-2:1; the plasticizer is a mixture of polyethylene glycol and dioctyl terephthalate with the mass ratio of 1:2-3:1; the lubricant is ester quaternary ammonium salt; the defoaming agent is an organosilicon quaternary ammonium salt defoaming agent.
Examples 1 to 12 of the sizing agent for low-twist electronic grade glass fibers of the present application are listed herein for more clearly explaining the technical scheme of the present application, wherein specific formulations of the respective components of the sizing agent for low-twist electronic grade glass fibers of examples 1 to 12 of the present application are shown in table 1.
Table 1 formulation of the impregnating compound of the example
Table 1 formulation of the impregnating compound of the examples
In examples 1 to 12, the high amylose starch used had a linear chain content of 50 to 70% and a hydroxyethyl modified amylopectin substitution degree of 0.02 to 0.20%.
The preparation method of the impregnating compound for the low-twist electronic grade glass fibers in examples 1 to 12 comprises the following steps:
adding high amylose starch and hydroxyethyl modified amylopectin starch into normal temperature water with the mass which is 5-10 times of that of the high amylose starch and hydroxyethyl modified amylopectin starch according to the preset mass ratio, stirring and dispersing, and then passing through a high temperature and high pressure digester until the high temperature and high pressure digester is heated to 110-130 ℃ and the pressure is increased to 2-5 kgf/cm 2 Then, steaming at the steaming flow of 800-1500L/h, and adding water accounting for 20-30% of the total mass of the impregnating compound to cool after steaming to obtain starch slurry;
adding an emulsifying agent and grease into water which is 5-8 times the mass of the grease at 60-75 ℃ according to a preset mass ratio, stirring for 30-60 min at a rotating speed of 1000-4000 rpm/min, adding a plasticizer with the preset mass ratio, and stirring to obtain a first emulsion;
adding the lubricant into water which is 10-20 times of the lubricant in mass and at 50-60 ℃ according to a preset mass ratio, and stirring to obtain a second emulsion;
adding the first emulsion and the second emulsion into starch slurry, supplementing the residual water, and then adding a defoaming agent and ammonia water according to a preset mass ratio to obtain an initial sizing agent;
the initial impregnating compound is kept at 100 kgf/cm to 200kgf/cm 2 Homogenizing under pressure by a homogenizer to reach qualified particle size of less than or equal to 5 μm to obtain the required impregnating compound.
It should be noted that the sequence of preparing the first emulsion, the second emulsion and the starch slurry can be adjusted according to the actual situation.
In addition, in order to better explain the effect of the present application, two kinds of impregnating compound formulations (comparative example 1 and comparative example 2) suitable for high-twist electronic grade glass fibers are selected as comparative examples, so as to facilitate the explanation of the technical scheme of the present application:
comparative example 1
The impregnating compound comprises effective components and water, the solid content is 6.663%, and the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein, the linear chain content in the high-amylose corn starch is 50-65%, 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 7.953%, and the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the linear chain content in the high amylose starch is 50-65%, and the substitution degree of the etherified modified amylopectin starch is 0.10-0.20%.
The preparation method of the comparative examples 1-2 comprises the following steps:
adding high amylose starch and hydroxyethyl modified amylopectin into normal temperature water with the mass of 5-10 times of that of the high amylose starch and hydroxyethyl modified amylopectin, stirring and dispersing uniformly, and then passing through a high temperature digester, and rising the temperature of the high temperature and high pressure digester to 110-130 ℃ and rising the pressure to 2-5 kgf/cm 2 Then, steaming at the steaming flow of 800-1500L/h, and adding normal-temperature water accounting for 10-20% of the total mass of the impregnating compound to cool after steaming to obtain starch slurry;
adding an emulsifying agent into melted grease, adding the melted grease into water accounting for 10 to 20 percent of the total mass of the impregnating compound at 65 to 70 ℃ for homogenizing and emulsifying, adding a plasticizer (comparative example 1)/a lubricant (comparative example 2), and stirring for 30 to 60 minutes to prepare emulsion;
adding the prepared emulsion into starch slurry, supplementing the residual water, finally adding ammonia water, and uniformly stirring to obtain the impregnating compound.
Performance test:
the production data of the examples and the comparative examples are controlled respectively, and the performance data of the examples and the comparative examples are subjected to comparative tests, and the test methods are as follows:
after the sizing agents of examples 1 to 12 and comparative examples 1 to 2 were formulated, they were coated on an electronic grade glass fiber G75 precursor product having a single fiber diameter of 9. Mu.m. The production test control ranges are shown in table 2:
table 2 production test method
| Oiling linear velocity (m/min) | 16～20 |
| Impregnating compound application temperature (. Degree. C.) | 60～68 |
| Cop oil (%) | 1.15～1.30 |
| Twist (twist/m) | 5～15 |
| Direction of twist | Z |
| Twisting machine spindle speed (rpm/min) | 2000～4500 |
| Twisting temperature (. Degree. C.) | 32～38 |
| Twist humidity (%) | 25～40 |
| Loom rotation speed (rpm/min) | 700～800 |
| Smoldering temperature (DEG C) | 400～600 |
| Open water pressure (kgf/cm) 2 ) | 0～40 |
Among them, to better illustrate the effects of the present application, comparative example 1 was subjected to a conventional twist test, and comparative example 2 was subjected to a low twist test; examples 1 to 12 and comparative example 1 all use a normal pressure water spray fiber opening mode, and comparative example 2 uses high pressure water jet fiber opening. The results of the performance tests of the examples and comparative examples are shown in Table 3.
TABLE 3 results of Performance test of examples and comparative examples
TABLE 3 results of Performance test of the impregnating compound of examples and comparative examples
| Project | Example 9 | Example 10 | Example 11 | Example 12 | Comparative example 1 | Comparative example 2 |
| Cop oil (%) | 1.26 | 1.25 | 1.26 | 1.26 | 1.16 | 1.20 |
| Cop moisture (%) | 0.05 | 0.04 | 0.05 | 0.04 | 0.03 | 0.03 |
| Twist (twist/m) | 6.3 | 7.2 | 8.4 | 8.1 | 22.3 | 8.1 |
| Stiffness (mm) | 95 | 93 | 97 | 93 | 93 | 86 |
| Cop average hairiness number (root) | 1.2 | 1.7 | 1.2 | 1.4 | 6.6 | 12.5 |
| Cloth cover defect (personal/myriad meter) | 14.8 | 14.4 | 13.0 | 17.4 | 29.6 | 60.5 |
| Warp and weft thread width (mum) | 627/638 | 625/620 | 627/623 | 623/627 | 591/609 | 573/587 |
| Thickness (mm) | 0.162 | 0.168 | 0.161 | 0.168 | 0.175 | 0.182 |
| Air permeability (cm) 3 /cm 2 /s) | 0.7 | 1.2 | 1.0 | 1.1 | 8.4 | 4.3 |
The performance test results in Table 3 show that the electronic grade glass fiber yarn produced by coating the low twist electronic grade glass fibers of examples 1 to 12 of the present application with the sizing agent has an oil content of 1.10 to 1.26%, a water content of 0.03 to 0.05%, a twist of 5.4 to 13.1 twists/m, and a stiffness of 92 to 97mm. The average hairiness of the cops of the electronic grade glass fiber yarns produced by coating the low-twist electronic grade glass fibers of the examples 1 to 12 with the impregnating compound is 1.1 to 2.1, and compared with the average 12.5 of the cops of the comparative example 2, the hairiness of the electronic grade glass fiber yarns with low twist is obviously reduced. The electronic grade glass fiber gauze produced by the impregnating compound for the low-twist electronic grade glass fibers of the embodiments 1 to 12 has 12.5 to 18.5 cloth surface defects per one thousand meters, and compared with the comparative examples 1 to 2, the electronic grade glass fiber gauze surface defects produced by the impregnating compound for the low-twist electronic grade glass fibers are greatly reduced. In addition, the warp and weft yarn widths of the electronic grade glass fiber yarns produced by the sizing agent for the low-twist electronic grade glass fibers in the embodiments 1-12 are higher than those of the comparative examples 1-2, and the thickness and the air permeability are lower than those of the comparative examples 1-2, which indicates that the electronic grade glass fiber yarns produced by the coating of the sizing agent for the low-twist electronic grade glass fibers are easy to open, and the air permeability and the thickness of the finished cloth are low, so that the cloth cover of the downstream process is favorably combined with the resin.
In summary, the formula and the preparation method of the sizing agent for the low-twist electronic grade glass fiber are scientific and reasonable, and all components in the formula are matched with each other, so that the defects of Mao Yugao, poor wear resistance and poor weaving performance in the production of the low-twist electronic grade glass fiber can be overcome, the production restriction is solved, the production efficiency of the low-twist electronic grade glass fiber can be improved, and the energy is saved.
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 (8)
1. The sizing agent for the low-twist electronic grade glass fiber is characterized by comprising an effective component and water, wherein the solid content of the sizing agent is 6.144-13.615%, and the effective component comprises a main film forming agent, grease, an emulsifying agent, a plasticizing agent, a lubricating agent, a defoaming agent and ammonia water; the solid mass of each effective component accounts for the total mass of the impregnating compound and is expressed as follows:
the main film forming agent is a mixture of high-amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high-amylose starch to the hydroxyethyl modified amylopectin is 1: 2-3: 2; the high amylose starch comprises high amylose tapioca starch or/and high amylose corn starch, and the linear content of the high amylose starch is 50-70%; the substitution degree of the hydroxyethyl modified amylopectin is 0.02-0.20%;
the grease is at least one of hydrogenated modified soybean phosphate grease, hydrogenated castor grease and hydrogenated peanut grease; the plasticizer is at least one of glycerol, polyethylene glycol, dioctyl terephthalate and dioctyl phthalate.
2. The sizing agent for low-twist electronic grade glass fibers according to claim 1, wherein the solid content of the sizing agent is 7.555-11.115%, and the percentage of the solid mass of each effective component to the total mass of the sizing agent is as follows:
the main film forming agent is a mixture of high-amylose starch and hydroxyethyl modified amylopectin, and the mass ratio of the high-amylose starch to the hydroxyethyl modified amylopectin is 1.5:2 to 2.5:2.
3. the sizing agent for low-twist electronic grade glass fibers according to claim 1 or 2, wherein the emulsifier is at least one of polyoxyethylene ether, polyurethane, and higher alkylamine.
4. The sizing agent for low-twist electronic grade glass fibers according to claim 1 or 2, wherein the lubricant is at least one of methyl octadecabonate, polyethylene polyamine, and esterquat; the defoamer is polyether modified organic silicon quaternary amine salt defoamer.
5. The sizing agent for low-twist electronic grade glass fibers according to claim 1 or 2, wherein the solid content of the sizing agent is 8.355-10.395%, and the percentage of the solid mass of each effective component to the total mass of the sizing agent is as follows:
wherein the main film forming agent is a mixture of high-amylose starch and hydroxyethyl modified amylopectin, the linear chain content of the high-amylose starch is 55-65%, and the substitution degree of the hydroxyethyl modified amylopectin is 0.05-0.10%; the grease is hydrogenated modified soybean phosphate grease; the emulsifier is a mixture of polyoxyethylene ether and polyurethane in a mass ratio of 1:2-2:1; the plasticizer is a mixture of polyethylene glycol and dioctyl terephthalate with the mass ratio of 1:2-3:1; the lubricant is ester quaternary ammonium salt; the defoaming agent is an organosilicon quaternary ammonium salt defoaming agent.
6. A method of preparing the sizing for low twist electronic grade glass fibers as defined in any one of claims 1 to 5, comprising the steps of:
adding the main film forming agent into normal-temperature water which is 5-10 times of the main film forming agent, stirring and dispersing, then passing through a high-temperature high-pressure digester, and after the high-temperature high-pressure digester is heated to a first preset temperature and is pressurized to a first preset pressure, cooking at a first preset cooking flow, adding warm water accounting for 20-30% of the total mass of the sizing agent after cooking is finished, and cooling to obtain starch slurry;
adding the emulsifier and the grease into water with the mass which is 5-8 times of that of the second preset temperature, stirring for a first preset time at a first rotating speed, adding the plasticizer, and stirring to obtain a first emulsion;
adding the lubricant into water with the mass which is 10-20 times of that of the third preset temperature, and stirring to obtain a second emulsion;
adding the first emulsion and the second emulsion into the starch slurry, supplementing the residual water, and then adding the defoaming agent and the ammonia water to obtain an initial impregnating compound;
homogenizing the initial impregnating compound under a second preset pressure by a homogenizer to reach qualified particle size, and obtaining the impregnating compound.
7. A low twist electronic grade glass fiber product produced from the low twist electronic grade glass fiber of any of claims 1-5 coated with a sizing.
8. Use of the low twist electronic grade glass fiber product of claim 7 in the manufacture of copper clad laminates and printed circuit boards.
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