CN1078684A - A kind of epoxy glass fibre insulating material and manufacture method thereof - Google Patents

A kind of epoxy glass fibre insulating material and manufacture method thereof Download PDF

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Publication number
CN1078684A
CN1078684A CN 92103281 CN92103281A CN1078684A CN 1078684 A CN1078684 A CN 1078684A CN 92103281 CN92103281 CN 92103281 CN 92103281 A CN92103281 A CN 92103281A CN 1078684 A CN1078684 A CN 1078684A
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China
Prior art keywords
glue
resin
glass fibre
compacting
product
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Pending
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CN 92103281
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Chinese (zh)
Inventor
凌恩永
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HUANENG ELECTRIC POWER GENERATION CO
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HUANENG ELECTRIC POWER GENERATION CO
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Priority to CN 92103281 priority Critical patent/CN1078684A/en
Publication of CN1078684A publication Critical patent/CN1078684A/en
Pending legal-status Critical Current

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Abstract

The present invention is a kind of flame retardant epoxy fiberglass insulation and manufacture method thereof that adopts vacuum pressing.Owing to add fire retardant, make the fire resistance of product can satisfy the specific (special) requirements of electric material.Glue contains melamine resin in the present invention, makes product have the arc resistance energy.And bonding functional of resin and fire retardant, glass fibre.Simultaneously because of having utilized epoxy resin impregnated glass fibre, and make the compacting environment be in vacuum state when moulding, this has just increased the electrical insulation characteristics of material, and makes the anti-bending of this material, impact strength height.The dielectric consume of this product is also few.So it is industrial that product of the present invention is widely used in electric material.

Description

A kind of epoxy glass fibre insulating material and manufacture method thereof
The present invention relates to a kind ofly form, and be impregnated with insulating materials and the manufacture method thereof of glass fibre by synthetic resin.Because it has characteristics such as the insulation of splendid height, fire-retardant and high strength, be widely used in electric, the exigent material industry of physical property.
By real production practices and documents and materials introduction as can be known, the manufacturing of electrically insulating material mostly divided for three steps finished.At first be to produce glue by certain prescription; Be gluing then, with resin impregnated glass fiber material; Be compression moulding under certain temperature, pressure at last.Specifically, the manufacturing of last glue all is to select the synthetic resin type for use according to producing needs, as various epoxy resins, amide-type, organic acid anhydride, unsaturated resin, phenolic resin, aminoplast etc., wherein be easy to get from raw material, can satisfy that general electric property requires and from considering economically, the most frequently used is epoxy resin, and all adopts cheap non-pure epoxy structure.The product that has is in order to increase are-tight property, and adopts the melamine-formaldehyde resin in the aminoplast.The character of glue has determined that it can not long preservation on the synthetic resin, thus all be supporting factory's preparation with gluing, suppression process, and be with using with production.For the photoresist coating process comparative maturity, polytypes such as vertical, horizontal are arranged, generally with horizontal in the majority, carry glue main body great majority alkali-free glass cloth, the specification of cloth, dipping glue quantity are determined with product is required.Glass cloth behind the impregnation, stacked putting together heated down in electricity (or steam) heat, and with the moulding of press cure under pressure, environmental pressure is a normal pressure.Product dispatches from the factory after tested.United States Patent (USP) 3.972.765 in 1976 has introduced a kind of " manufacture method of the used laminate of printed circuit " and has made the water soluble phenolic resin with phenol and formolite reaction earlier, then with silane and this resin in the water-soluble and ethanol, handle the non-woven glass fibre fabric, after drying, use the above-mentioned non-woven glass fibre fabric of epoxy resin solution (epoxy resin, dicyandiamide, benzyl dimethylamine are dissolved in MEK and the propane diols) dipping again.At last, a stator number is superimposed together, at 80 ℃, under pressure 20 kg/cm, hot pressing and obtain laminate.This laminate insulaion resistance is 1~5 * 10 15Ohm reduces to 1~5 * 10 after boiling water treating 10Ohm, and matrix do not bleach, and illustrates that adhesive is not dissolved, and glass fibre can not separate with epoxy resin.But, above-mentioned laminate product, for the industrial materials electric, that physical property is all had relatively high expectations, but be difficult to meet consumers' demand, should insulating properties superior as product, the intensity height has certain flame-retardant nature again, the arc resistance energy just must improve, improve the production technology of existing product.
The objective of the invention is to avoid above-mentioned weak point of the prior art and provide a kind of and adopt vacuum pressing, make with melamine-formaldehyde resin and epoxy resin glue and fire retardant, the intensity height, the epoxy glass fibre insulating material with superior electrical performances such as fire resistance and other arc resistance are good.
Purpose of the present invention can reach by following measure.We answer the requirement of user and department, develop on the prior art basis.Insulating materials of the present invention is also finished by resin manufacturing, photoresist coating process and compacting three road technologies.The manufacturing of resin liquid we to adopt melamine-formaldehyde resin be base-material, this resin can increase the are-tight property of product, in the manufacturing of this resin, to choose butanols be solvent through screening us, and in the prior art, the manufacturing of this resin liquid, solvent is an ethanol.This is because the adding of butanols, to the effect that the are-tight resin of follow-up adding has the dissolving of assisting and disperses, make product are-tight effective, the life-span is long.After making above-mentioned resin liquid, add epoxy resin (E-51) and fire retardant, curing agent, solvent acetone again, making code name is glue on the NZHB type, makes product insulating properties, intensity higher, and has fire resistance.The melamine-formaldehyde resin that we adopt and the adhesivity of fire retardant are also fine.Then, glass cloth is carried out gluing.In final operation, during compacted products, for making the product quality firm, the intensity height, last glue is better to soaking into of glass fibre, eliminates volatile matter, bubble etc. simultaneously effectively, the present invention has adopted the vacuum pressing method especially, heating, under the pressurized conditions, utilizing vacuum equipment that environment is caused vacuum, vacuum is in 0.04~0.1MPa(MPa) between.The vacuum pressing method has significantly reduced the remaining quantity of solvent and bubble, has improved the intensity and the boiling water resistance energy of laminate.
Purpose of the present invention can also reach by following measure.When producing melamine-formaldehyde resin liquid, at first be that solvent butanols, formaldehyde are added reactor, warming while stirring under normal pressure when temperature reaches 60 ℃, slowly adds melamine, and is warming up to proper temperature to emulsification and kept approximately 30 minutes.Press formula ratio then and add phthalic anhydride, 3.5~4 hours retention times, naturally cool to 60 ℃ afterwards.Earlier lower layer of water is abandoned after the reactant layering, carried out vacuum dehydration again, vacuum is about 0.06 MPa.Dehydration finishes, and the butanol solution of resin glue is waited to make NZHB and gone up glue.The material formula that adds of resin glue is: melamine 7~15%, formaldehyde 40~60%, butanols 40~60% all are weight percentage (down together).Glue (NZHB) must be melt into liquid state with E-51 epoxy resin and the heating of bromination epoxy fire retardant earlier before on system.Epoxy resin, fire retardant, curing agent (THPA), acetone solvent and the above-mentioned resin liquid that makes are added reactor, stir and be heated to 80 ℃, add the benzyl dimethylamine catalyst then, after holding time 2~3.5 minutes, promptly get NZHB and go up glue.Glue primary raw material prescription is an E-51 epoxy resin 20~35% in the manufacturing, fire retardant 15~25%, acetone 10~20%, resin liquid 10~20%, benzyl dimethylamine 0.1~0.5%, curing agent 15~25%.Should go up glue owing to reasons such as autohemagglutination, curing, storage period must not be above three days.Last glue process device therefor is horizontal gluing machine, the aforementioned glue of going up is added in the gluing machine, be warming up to 100~150 ℃, make glass fabric pass through last glue, should control glue content at any time when gluing, should contain glue 36~45%, solvable resin content is more than 90%, volatile matter is adjusted the operating procedure condition of gluing machine at any time below 1% according to this index.Gone up the glass fabric of glue, preferably in time removed presswork,, then must not surpass two days later as preserving.
The finished product suppression process of gluing glass fabric is also very important, with the fiber cloth that cuts, put into hot-die, look production board desired thickness configuration sheet number, generally be odd number collocation, can suppress 1~5 production board at every turn, surpass 5 then because of the control of temperature, pressure, the uniformity coefficient of heating is had any problem, and is difficult to ensure the quality of products.Each opens production board before compacting, between to separate with the corrosion resistant plate that both sides accompany polypropylene film, one side topmost and the bottom contact hot-die respectively spread several brown paper.At first give heat with steam, temperature reaches 100~120 ℃, pressure rises to 20 kg/cm gradually, give 10~15 minutes hot time, heat then to 180 ℃, pressure rises to 50~60 kg/cm, kept this temperature and pressure 4 hours (every production board is below 3 millimeters), the finished product thickness of slab surpasses 3 millimeters, 1 millimeter of every increase thickness of slab, and the heat-insulation pressure keeping time increases by 20 minutes.Naturally cooled off 30 minutes then, with logical steam pipe, be cooled to normal temperature again, be finished product after the discharging through valve conversion water flowing.Hot press up and down two heating platens is designed to hollow, on put jet chimney, produce 10~13 kilograms of high steams as the heating thermal source with boiler.The steam pipe side is cooled off and is used with the other water pipe that connects of valve.In this technology, the hot press surrounding environment will keep vacuum from start to finish, and vacuum is 0.04~0.1MPa.Therefore, use the steel plate welded seal around the hot press, whole high about 2 meters, long 2 meters, wide 1.5 meters, door of positive design, with the rubber cushion sealing, a window is opened in the side around the door, observes laminate compacting situation.Design one passage above, on connect valve in order to get rid of vacuum.A logical vavuum pump pipeline is installed simultaneously.This method still can adopt other hot-die to suppress the dielectric panel that some other has certain flexibility shape according to different requirements except that can pressed sheet.
With the compacting slab insulant embodiment is described below the present invention.When making 3 millimeters thick flame retardant type electrical insulation glass laminated web, the better charge ratio of resin liquid manufacturing is: melamine 9%, formaldehyde 45%, butanols 46%.During glue, better prescription is: E-51 epoxy resin 28%, bromination epoxy fire retardant 18%, acetone 15%, resin liquid 18%, benzyl dimethylamine 0.3%, curing agent 21% on making NZHB.In the last glue process, the gluing temperature can adopt 150 ℃, and after the gluing, the glass fabric gel content is controlled at 36%, and solubility resin content is greater than 90%, and volatility is below 1%.When the neutralizing layer stampings, the laminate of 3 millimeters thick adopts adhesive plaster on 19 layers of glass fibre, under the our factory heated press conditions, once can suppress five laminates, vacuum degree control is at 0.04MPa, heating steam is with the steam of 10 gauge pressures, and giving hot temperature is 120 ℃, and the time needs 15 minutes approximately.When boosting to 60 kg/cm processes, also vacuumize to make and reach 0.04MPa with connecing vacuum-pump line simultaneously, simultaneous temperature rises to 180 ℃, can stop vavuum pump then, insulation, pressurize 4 hours.Observe the compression moulding situation by visor.Naturally cool off then, and eliminate vacuum state by passage with valve, last available running water is cooled to normal temperature.Glass fibre laminated product specification is: 1.1 meters * 1.6 meters.Suppress five plates.Some process conditions of not mentioning one of embodiment are the condition in the literary composition as described above.Raw material proportionings required for the present invention etc. all refer to the industrial goods specification.
The present invention has the following advantages compared to existing technology: this product is owing to being added with fire retardant, so good flame retardation effect can satisfy the specific (special) requirements of some electric material. Used melamine-formaldehyde resin, take butanols as solvent, arc resistance can be good, and through practical proof: it and epoxy resin intermiscibility are good, and be good with the cohesive of glass fibre. Glue on the adapted epoxy resin system in addition adopts the Vacuum Pressure method for making again, remaining bubble and the volatile substance that made product eliminates, and electrical insulation capability is good, strength increase. This product can bear machining, to adapt to the requirement of electric material assembling. Product of the present invention is through industrial endurance, process, and through the test of supervisor's testing department. Below we are developed the performance of product, detect data with relevant product standard and representative products both domestic and external and compare, be listed as follows:
Project Unit Enterprise's mark EPGCl West Germany's sample Japan's sample My wide sample measured data
Perpendicular layers is to bending strength MPa ≥340 ≥340 394 412 426
Impact strength KJ/M ≥37 ≥37 37.4 41.9 82
Perpendicular layers 1min in 90 ± 2 ℃ of transformer oil of anti-arc stiffness KV/M 12.5 11.5 19.6 13.8 Qualified
Parallel layers 1min in 90 ± 2 ℃ of transformer oil of proof voltage KV 37 35 38 43 Qualified
Insulaion resistance after the immersion Ω 〉5×10 10 ≥5×10 10 1.5 10 10 2.3 10 12 3.9×10 15
1MHZ loss factor after the immersion ≤0.04 ≤0.04 0.032 0.022 0.02
1MHZ relative dielectric constant after the immersion ≤5.5 ≤5.5 5 4 4.8
Water imbibition mg ≤10 ≤22 3.8 2.7 4.2
Flammable (FV method) Level FV1 Do not have Not fire-retardant FV1 FV1
Arc resistance S 120 Do not have 175 135 125

Claims (6)

1, a kind of last glue made from synthetic resin, make after the glass fibre gluing insulating materials of row compacting again, it is characterized in that producing melamine-formaldehyde resin liquid as solvent with butanols, and then add E--51 epoxy resin and bromination epoxy fire retardant, acetone, curing agent, the benzyl dimethylamine catalyst makes glue, glass fibre is after last glue gluing, under vacuum environment, be pressed
2, the insulating materials of usefulness synthetic resin glue impregnated glass fiber compacting according to claim 1 when it is characterized in that making melamine-formaldehyde resin liquid, adds material formula and is: melamine 7~15%, and formaldehyde 40~60%, butanols are 40~60%,
3, the insulating materials of usefulness synthetic resin glue impregnated glass fiber compacting according to claim 1, the composition of raw materials that it is characterized in that glue on the glass fibre is: E-51 epoxy resin 20~35%, fire retardant 15~25%, acetone 10~20%, resin liquid 10~20%, benzyl dimethylamine 0.1~0.5%, curing agent 15~25%
4, the insulating materials of usefulness synthetic resin glue impregnated glass fiber compacting according to claim 1 is characterized in that, during glass fiber impregnated gluing, should control spread is 36~45%, and solubility resin amount is more than 90%, and volatile matter is below 1%,
5, a kind of last glue made from synthetic resin, make the glass fibre gluing after, the insulating materials manufacture method of row compacting again, should heat when compression moulding, the machinery pressurization is characterized in that when compacting, at first use steam preheating, 100~120 ℃ of temperature, forcing press is forced into 20 kg/cm, 10~15 minutes preheating time, heat then to 180 ℃, pressure rises to 50~60 kg/cm, heat-insulation pressure keeping 4 hours (every formation of lots plate 3 millimeters thick), cooling then.The hot press environment keeps vacuum state from start to finish in pressing process, vacuum 0.04~0.1MPa,
6, as the manufacture method of the compacting of the usefulness synthetic resin glue impregnated glass fiber as described in the claim 5 insulating materials, it is characterized in that using the steel plate welded seal around the hot press, high about 2 meters for keeping the environment vacuum state, wide about 1.5 meters, be about 2 meters, the front is opened one, studs with rubber cushion around the door, a window is opened in the side, top connects a passage with valve, and is hinged with a vacuum pipe, external vavuum pump.
CN 92103281 1992-05-09 1992-05-09 A kind of epoxy glass fibre insulating material and manufacture method thereof Pending CN1078684A (en)

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CN 92103281 CN1078684A (en) 1992-05-09 1992-05-09 A kind of epoxy glass fibre insulating material and manufacture method thereof

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Application Number Priority Date Filing Date Title
CN 92103281 CN1078684A (en) 1992-05-09 1992-05-09 A kind of epoxy glass fibre insulating material and manufacture method thereof

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CN1078684A true CN1078684A (en) 1993-11-24

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100366423C (en) * 2005-08-31 2008-02-06 李军 Inorganic wet curtain and its prepn. method
CN102307920A (en) * 2009-02-05 2012-01-04 阿科玛股份有限公司 Fibers sized with polyetherketoneketones
CN104943162A (en) * 2015-05-05 2015-09-30 上海和鸣变压器有限公司 Glass steel barrel manufacturing technology for superconducting transformer
CN106319795A (en) * 2016-08-31 2017-01-11 中国西电电气股份有限公司 Method for impregnating epoxy glass fiber yarn with epoxy resin
CN110561801A (en) * 2019-09-16 2019-12-13 昆山圣达保持架有限公司 Manufacturing method of melamine fiber tube for fuse
CN112226168A (en) * 2020-09-14 2021-01-15 深圳日高胶带新材料有限公司 Roller-stacked coated insulating antistatic cloth-based adhesive tape and manufacturing method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100366423C (en) * 2005-08-31 2008-02-06 李军 Inorganic wet curtain and its prepn. method
CN102307920A (en) * 2009-02-05 2012-01-04 阿科玛股份有限公司 Fibers sized with polyetherketoneketones
CN104943162A (en) * 2015-05-05 2015-09-30 上海和鸣变压器有限公司 Glass steel barrel manufacturing technology for superconducting transformer
CN106319795A (en) * 2016-08-31 2017-01-11 中国西电电气股份有限公司 Method for impregnating epoxy glass fiber yarn with epoxy resin
CN110561801A (en) * 2019-09-16 2019-12-13 昆山圣达保持架有限公司 Manufacturing method of melamine fiber tube for fuse
CN112226168A (en) * 2020-09-14 2021-01-15 深圳日高胶带新材料有限公司 Roller-stacked coated insulating antistatic cloth-based adhesive tape and manufacturing method thereof

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