CN102775071A - Manufacture technology for surface-coarsened glass fiber - Google Patents
Manufacture technology for surface-coarsened glass fiber Download PDFInfo
- Publication number
- CN102775071A CN102775071A CN2011101201324A CN201110120132A CN102775071A CN 102775071 A CN102775071 A CN 102775071A CN 2011101201324 A CN2011101201324 A CN 2011101201324A CN 201110120132 A CN201110120132 A CN 201110120132A CN 102775071 A CN102775071 A CN 102775071A
- Authority
- CN
- China
- Prior art keywords
- erosion
- spun glass
- stung
- fiberglass surfacing
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a technology for improving adhesion between glass fiber and a resin, employing a chemical method for etching and coarsening surfaces of the glass fiber to make the adhesion between the glass fiber and the resin better, thereby greatly improving manufacturing technology level of raw materials of electronic components. Printed circuit boards and IC packaging substrates which are manufactured by the materials have better product yield and higher manufacturing capacity, and can meet rapid development demands of electronic industry.
Description
Technical field
Printed circuit board is maximum in an ordinary electronic product components and parts, and it is the carrier that is carrying various electronic devices and components and making the connection of mutual maintenance certain way between them, thereby realizes the design functions of use of electronic product; The IC encapsulating carrier plate; Then be important electron components and parts in the ic component; It is the carrier of wafer, make between the wafer and wafer and other electronic devices and components between keep being connected of certain way each other, thereby realize the design functions of use of ic component.The main starting material of electronic devices and components such as printed circuit board and IC encapsulating carrier plate---copper-clad plate and partly change cured sheets; Mainly constitute by materials such as Copper Foil, resin, glasscloths; The manufacturing technology level of spun glass directly has influence on the final quality and the state of the art of these electronic devices and components, so the manufacturing of spun glass is very important in an electronic industry industrial chain link.
Background technology
The conventional glass fiber all is from the glass furnace of high temperature melting, to pull out filament, and many filaments are twisted with the fingers into one, again one one fiber is made into the cloth shape, can become the glasscloth that we are commonly called as.Glasscloth is through after a series of processing; Carry out the resin impregnation; After containing the spun glass process low-temperature bake that is soaked with resin; Become the flaky substance of semi-cured state, promptly prepreg (English abbreviates as: PP), cover with Copper Foil and impose HTHP again by the prepreg two sides; Just can become the main starting material of printed circuit board: copper-clad plate, printed circuit board or IC encapsulating carrier plate are made through a series of processing treatment after high-temperature high-pressure lumps together by the copper-clad plate of having made figure and prepreg again.From the glass furnace of high temperature melting, pull out thin glass yarn; Its surface is slick; Though through series of physical and chemical treatment; But the bonding force between its surface and the resin can not reach very high level eventually, can not satisfy the demand of the electronic industry of world's high speed development, is the urgent work of industry so improve constantly the manufacturing technology level of copper-clad plate.The present invention relates to a kind of technology that how to improve the bonding force between glasscloth and the resin; Thereby can be so that the manufacturing technology level of the important raw and processed materials of printed circuit board or IC encapsulating carrier plate be gone on a new step, with the demand of the electronic industry that satisfies high speed development.
Summary of the invention
The technical problem that the present invention solves is: according to the existing manufacturing technique level, the bonding force between resin and the spun glass is limited, thereby causes the manufacturing technology of printed circuit board further to develop.The present invention controls from the production process of raw material, has improved the bonding force between resin and the spun glass, makes the starting material of electronic product obtain the more development of hi-tech, satisfies the demand of the electronic industry of world's high speed development.
Technical scheme of the present invention is: the spun glass manufacturing technology that a kind of surface coarsening is provided; It is characterized in that; To being applied to starting material such as prepreg necessary in the electronic devices and components such as printed circuit board and IC encapsulating carrier plate in the electronic product and copper-clad plate, before these starting material of preparation, will constitute one of these raw-material essential substance: spun glass; It is coarse that the method that adopts chemical erosion is stung erosion with the surface of spun glass, to improve the bonding force between spun glass and the resin.
Further technical scheme of the present invention is: adopt the pharmaceutical chemicals that contains fluorine that fiberglass surfacing is stung erosion, thereby make that more slick originally fiberglass surfacing becomes coarse.
Further technical scheme of the present invention is: sting erosion spun glass adopted to contain and minimumly in the fluorine chemistry medicine comprise hydrofluoric composition.
Further technical scheme of the present invention is: stinging the erosion fluorine-containing pharmaceutical chemicals that spun glass adopted is minimum a kind of material that is in gaseous phase.
Further technical scheme of the present invention is: earlier spun glass is carried out long high bake, employing afterwards has the tart pharmaceutical chemicals fiberglass surfacing is stung erosion, thereby makes that more slick originally fiberglass surfacing becomes coarse.
Further technical scheme of the present invention is: sting and lose the minimum composition that comprises hydrogenchloride in the tart pharmaceutical chemicals that has that spun glass adopted.
Further technical scheme of the present invention is: sting and lose the minimum H of comprising in the tart pharmaceutical chemicals that has that spun glass adopted
2SO
4Composition.
Further technical scheme of the present invention is: this technological minimum following step that comprises: boil off → fiberglass surfacing is stung erosion alligatoring → silicon alkane coupling and is handled.
Further technical scheme of the present invention is: this technological minimum following step that comprises: boil off → open fine processing → fiberglass surfacing to sting erosion alligatoring → silicon alkane coupling processing.
Further technical scheme of the present invention is: before silicon alkane coupling treatment step, fiberglass surfacing is stung the erosion roughening treatment.
Further technical scheme of the present invention is: after drawing out spun glass, before the sizing treatment step, fiberglass surfacing is stung the erosion roughening treatment.
Further technical scheme of the present invention is: minimumly in the treating processes of fiberglass surfacing being stung the erosion alligatoring comprise following substep: sting erosion → cleaning → oven dry.
Further technical scheme of the present invention is: minimumly in the treating processes of fiberglass surfacing being stung the erosion alligatoring comprise following substep: sting erosion → cleaning.
Further technical scheme of the present invention is: it is coarse that the method that adopts chemical erosion is stung erosion with fiberglass surfacing, stings erosion and advance the degree of depth of fiberglass surfacing and be controlled between 1%～20% the scope that accounts for glass fiber diameter.
The effect that the present invention obtains is: alligatoring is carried out on the surface through to spun glass, thereby has improved the bonding force between resin and the spun glass, makes the starting material of electronic product obtain the more development of hi-tech, satisfies the demand of the electronic industry of world's high speed development.
Description of drawings
Fig. 1 is one of the process flow sheet of the spun glass manufacturing technology of surface coarsening.
Fig. 2 be surface coarsening the spun glass manufacturing technology process flow sheet two.
Fig. 3 is one of particular flow sheet of " fiberglass surfacing is stung the erosion alligatoring " technology.
Fig. 4 is two of the particular flow sheet of " fiberglass surfacing sting erosion alligatoring " technology.
Spun glass and the surperficial segment synoptic diagram thereof of Fig. 5 for not passing through alligatoring.
Spun glass and the surperficial segment synoptic diagram thereof of Fig. 6 for passing through alligatoring.
Embodiment
Below in conjunction with the practical implementation example, technical scheme of the present invention is further specified.
Spun glass: glass is a kind of mixture, and its definition is " inorganics is after the high temperature melting mixes, and cooling becomes a kind of hard objects of noncrystalline kenel again ".Is drawn into filaments (Filament) as a textile fiber material in the development of new uses for success in 1939 formally entered the era of glass fibers.Spun glass can be divided into two kinds of situation: a kind of is continous way, is used to weave glass cloth (Cloth or Fabric); Another kind is discontinuous fixed length formula, and slabbing glued together is called glass seat (Mat).Many glass fiber compositions are a branch of, and glass fiber is pressed warp-wise and broadwise interlacing Cheng Buzhuan one by one again, can obtain glasscloth.
Glasscloth used in copper-clad plate (English abbreviation: CCL) with printed circuit board (English abbreviation: PCB) on the industry in the market; Grade is that E-Grade is the electronic-grade material, and it is the cloth shape material that is woven and be made into through a series of processing by the electronic-grade glass yarn.Glasscloth kind commonly used has 7628,2116,1080 etc., and it be a code name, the digital meaning of no essence.Detail specifications and forming as follows:
Original spun glass making process has: moisture regain, and------heald frame--is gone up weft yarn----boil off--grey cloth check--the silicon alkane processing-inspection after construction etc. of weaving cotton cloth to sizing to warping.Specify as follows:
Moisture regain: the extremely crisp and easy fracture of former glass, it is unusual when next operation, to be prone to produce filoplume, broken silk, broken yarn etc., handles so before coming into operation, will pass through moisture regain.The purpose is to allow a resurgence of moisture condenses into water film on the glass surface, glass fiber enhanced flexibility.
Warping: glasscloth be by warp thread (Warp) and weft yarn (Fill) be interwoven in length and breadth, because of the length of warp thread is very long, concerning the overall quality of cloth.So need the just cloth fabric width degree that weaves, with the raw yarn bought again in addition close interval arrange, just again with multireel raw yarn while parallel around wait weave cotton cloth on axle (Warp beam).Weft yarn then be directly on cop (Qvill or bobbin) going to weave cotton cloth gets final product.Because warp thread is through arrangement, and the yarn number is also many than weft yarn, so endurance strength is all good than weft yarn, thereby the stressed bigger direction of printed wiring board, should be advisable with warp-wise.
Sizing: sizing is the warp thread of arranging compiling again, and the processing (Sizing) that also will do a starching is called " slurry warp ".The purpose is to increase lubrication and reduce friction.These slurries also want destarch to handle after being made into cloth, to obtain clean glass surface.The Tension Control that this kind starching is handled is wanted SC, in case its fracture and influence the quality of cloth.The last warp thread of crossing slurry also will squeeze wheel (Nip Roll) through one and squeeze out redundant sizing agent, and then through after the oven dry of heat steam, can carry out the operation (Entering) of heald frame.
Heald frame: claim to combine yarn again.This action is every warp thread all to be penetrated the steel of taking the lead smash, and enables that (Loom) carries up and down in loom.Simultaneously, also need go up weft yarn, last weft yarn be original-pack living yarn again directly on cop; When weaving cotton cloth by " shuttle " or compressed-air actuated drive; Back and forth run quickly between warp thread, and form passing through and interweave one on the other with it, the preparation of weaving cotton cloth has been accomplished in various pre-treatments to this.
Weave cotton cloth: the method for weaving cotton cloth commonly used at present is the shuttle less loom method that drives the weft yarn yarn with compressed air or water.The method of weaving cotton cloth has multiple different types, but is used for the glass cloth of substrate, but from start to finish all only with a kind of flat weaving method soon through the weft yarn up and down weaving, the tool stability of the size of its cloth of flat weaving method is also least yielding, and weight and thickness are also the most even.
Boil off: claim to burn clean again.When glasscloth has woven completion, will to obtain clean glasscloth, make it can do further silicon coupling again and handle removing for the convenient slurry of temporarily coating of processing procedure.Because of glasscloth can not burn, but the organism that its adhering on surface can be decomposed into gas and break away from the glasscloth that so can obtain cleaning.Usually can be divided into the processing of two steps, at first be that continuous aerobic burns, and furnace temperature reaches 593～816 ℃, can burn 91～98% slurry, and then long-time low temperature batch processing; Next is that discontinuous batch of formula handled, and it is the glass cloth overline to be wrapped on the metal cylinder of porous put in the baker again, in 260 ℃～371 ℃, burns 55～80 hours, and the organic matter in the cloth is not approachingly had by further evaporating into fully.Batch formula subzero treatment method is slowly left grease and fugitive constituent in the slurry, unlikelyly causes great amount of heat energy to pour in and generates the reduction that tensile strength should be arranged.
The grey cloth check: in this step, adopt the mode of manual checking, fully whether the quality of affirmation glasscloth conformance with standard, for incongruent product, need choose, or graduation is handled.
Silicon alkane is handled: claim silicon alkane coupling processing again.Because glass surface is very slick, other material such as water, resin etc. are not easy glass surface or fiberglass surfacing wetting well, just can not combine well between resin and the spun glass like this, thereby produce quality problem.Silane treated glass fiber surface is coated with a "coincidence" of the cortex, so that the resin in addition to the original mechanical properties, and then provide a molecular level "bond relay", drastic changes in temperature to maintain a combination of both strength , it can be called "adhesion promoter" (Adhesion? promoter).If silicon alkane processing layer can protective glass the surface, make its unlikely sticking power that loses with resin under the encirclement of moisture content, and then can keep the insulativity of dielectric material.This kind coupling agent is essentially a kind of material that blendes together (Hybrid Material), and an end has the very strong organic functional base of a kind of reagency in its molecule, and the other end then is the functional group of inorganic nature, and is middle then be the trunk of silicon alkane.The in-between unimolecular layer of this kind " coupling epithelium " has promptly formed at the film of B-stage intact man-hour.If the above silanes which compound coupling agent such as molecular structure: X-Si-R-(OCH3) 3, X is amino group, an epoxy group, and styrene.
So original spun glass is made the problem that exists: because spun glass is exactly slick originally; Though passed through a series of course of processing; And passed through silicon alkane and handled; But the smooth property of fiberglass surfacing does not change, and the bonding force between resin and the spun glass can cause its bonding force size can only reach some values because of the slick characteristic of fiberglass surfacing, is difficult to upwards break through again.People have thought that thousand and one way goes to improve this bonding force and combines effect at present; As adjust the prescription of resin, but the formula rate in the just simple adjustment resin has no idea to reach and improves this bonding force, and only variation has taken place in the kind of resin; Promptly adopted more fine resin kind; Bonding force has just got on naturally like this, but the consequence that such way can bring raw-material cost also to rise greatly simultaneously, this has no idea to apply on a large scale.Also have after the glasscloth boil off, having adopted increases the water spray needle punching (English is: Water Jet Needling) reprocess, warp thread and weft yarn are exposed in the part of cloth cover evenly open fibre, the formation flats.According to the depth of processing stage, can this cloth be divided into two types: only open fibre for one type; Another kind of except outside the fibre, also fluff (partly single wire fracture) through weft yarn, make cloth cover form the fine and closely woven fine hair that one deck evenly gathers, so be referred to as nylon loop.And in the simple glass cloth without the water spray processing treatment, the tight obvolvent of the single strand in warp thread and the weft yarn, through weft yarn crossover portion protuberance, quadrangle becomes the space.Open fine cloth and nylon loop because ORGANDY is released shakeouts, obviously slow down through the projection of weft yarn crossover portion, the space is inaccessible or dwindle, thereby the cloth cover smoothness improves greatly.Spun glass through such processing; Bonding force between resin and the spun glass also can obtain to increase; And cost can significantly not increase yet; But through after such processing, still can't satisfy electronic product growing and to the requirement that constantly becomes strict of raw-material technical characterictic.
So the solution that proposes among the present invention is, before carrying out silicon alkane coupling processing; With fiberglass surfacing sting the erosion coarse; Contact surface between resin and the spun glass increases greatly, and the bonding force between them has also just increased naturally greatly, and cost does not have too big amplification.Below provide and how to realize fiberglass surfacing is stung the coarse concrete scheme of erosion.
Sting erosion scheme one: adopt the pharmaceutical chemicals that contains fluorine that fiberglass surfacing is stung erosion, thereby make that more slick originally fiberglass surfacing becomes coarse.Fluorine-containing material can corrode the material of category of glass; Thereby cause the effect of etching; And hydrogen fluoride is the most frequently used and more facile a kind of material; Hydrogen fluoride and all can the material of category of glass be corroded with the mixture of other materials is so containing of stinging erosion spun glass adopted minimumly in the fluorine chemistry medicine comprises hydrofluoric composition and promptly can realize the erosion of stinging to glass.Stinging erosion fluorine-containing pharmaceutical chemicals that spun glass adopted can be to be in liquid material, also can be to be in the gasiform material, if during fluent meterial, needs glass fiber is immersed in the fluorine-containing liquid, to realize the erosion of stinging to spun glass; If during gaseous substance, need glass fiber is placed fluorine-containing gas, to realize the erosion of stinging to spun glass.The benefit that adopts gaseous substance to sting erosion is, stings after erosion finishes, and can dry, and spun glass is still exsiccant; If when adopting fluent meterial to sting erosion; Spun glass or glasscloth itself understood impregnation and adhered to liquid; The next treatment process that can be transported to these liquid causes the pollution of operation down, and in the process of transporting, the fluorine-containing material that is contained in the liquid can continue to sting the erosion spun glass; Cause that to sting erosion inhomogeneous or out of control, be unfavorable for producing and steadily carry out.The more important thing is; Spun glass is not easy to be soaked into by fluent meterial; Local location maybe by soaked with liquid to and cause stinging the erosion poor or basic just not stinging lost, such result does not play the effect of processing, the quality of product also is not assurance.If adopt gaseous substance to sting the erosion spun glass, when spun glass is placed in the gaseous state fluorine-containing material, will be snapped erosion at once, there is not the problem that can't soak into.In addition, adopt the gaseous state fluorine-containing material to sting the erosion spun glass, can also make that the surface of spun glass is more coarse, thereby make the bonding force between spun glass and the resin more strengthen.Strict control is stung the degree of depth that erosion advances fiberglass surfacing accounting between 1%～20% the scope of glass fiber diameter, can obtain alligatoring effect preferably, and can not cause other problems.Shown in 1 among Fig. 5, the 1st, do not pass through the pulsating synoptic diagram of the spun glass of roughening treatment, its surface is slick; As shown in Figure 6,1 passed through roughening treatment after, its surface becomes more coarse; A and b are illustrated respectively in the erosion amount of stinging of upper and lower two positions of fiberglass surfacing; Under the normal production conditions, a is to equate basically with b, and this stings the erosion amount and is controlled between 0.02 micron to 2 microns and gets final product.In process of production, the gaseous state fluorine-containing material need cooperate with suitable agitating or blowing, so that spun glass is in the uniform gaseous state fluorine-containing material of the concentration space, is beneficial to the carrying out that stings the erosion reaction simultaneously.Also have, fluorine-containing material is a hazardous and noxious substances, cannot directly be discharged in the air or in the external environment, needs to cooperate with enough recovery systems to accomplish such purpose.
Sting erosion scheme two: employing has the tart pharmaceutical chemicals fiberglass surfacing is stung erosion, thereby makes that more slick originally fiberglass surfacing becomes coarse.Sting and lose the material that the tart pharmaceutical chemicals can adopt the composition that comprises hydrogenchloride that has that spun glass adopted, also can adopt to comprise sulfuric acid (H
2SO
4) or other sour compositions, or by the material that more than one acid mixes, in stinging the erosion process, need to cooperate with suitable heating, sting the process of erosion spun glass to quicken alligatoring.
We know that the composition that constitutes glass mainly contains following: SiO
2, Al
2O
3, B
2O
3, CaO, MgO, R
2O, the produced glass of normal condition, these compositions can be mixed equably, form whole uniformly formation, promptly belong to the glass of not phase-splitting.As glass is heat-treated under 400～650 ℃ of temperature, it can be transformed into Na
2O-B
2O
3With SiO
2Two phases, i.e. the glass of phase-splitting.Make the granularity of glassy phase of glassy phase and the silicic acid matter of boronic acid containing and alkalimetal oxide be about the order of magnitude of tens dusts, form two kinds of glassy phase miscellaneous fine structures, such glass under 90 ℃ with processing such as hydrochloric acid and hot water, the Na of solubility
2O-B
2O
3Glassy phase is dissolved out, and remaining just becomes with SiO
2Be major ingredient, it is the glass with micropore shape that has kept original shape of glass, and its surface promptly has coarse characteristic.Certainly, also can adopt and contain sulfuric acid or other sour solution is done this processing, but processing speed can be slow.According to use occasion and needs, control the variation of heat treatment time and temperature etc., can change aperture, pore distribution, the pore volume of micropore, process the micropore of aperture homogeneous.Excess processes can cause the Na of solubility in the whole spun glass
2O-B
2O
3Glassy phase all is snapped eating away, makes spun glass become the vesicular strand shape material as the sponge shape, and not only physical strength descends greatly and cannot meet the demands; And the as easy as rolling off a log moisture absorption and storage pollutent; In the manufacturing processed of printed circuit board, the moisture absorption can cause printed circuit board itself to have steam, can run into processing such as water and need baking in the mill in the journey repeatedly; Thereby water evaporates goes out to cause problems such as plate bursting, layering during baking, and a large amount of quality problem will be following.Strict control is stung the degree of depth that erosion advances fiberglass surfacing and is being accounted between 1%～20% the scope of glass fiber diameter; Both can obtain coarse fiberglass surfacing; Can guarantee again follow-up quality problem not to take place, thereby meet the use of printed wiring board industry.Shown in 1 among Fig. 5, the 1st, do not pass through the pulsating synoptic diagram of the spun glass of roughening treatment, its surface is slick; As shown in Figure 6,1 passed through roughening treatment after, its surface becomes more coarse; A and b are illustrated respectively in the erosion amount of stinging of upper and lower two positions of fiberglass surfacing; Under the normal production conditions, a is to equate basically with b, and this stings the erosion amount and is controlled between 0.02 micron to 2 microns and gets final product.
For the control of stinging the erosion amount between 0.02 micron to 2 microns, can require and set the different erosion amounts of being admitted to according to the spun glass size of different diameter, different alligatoring degree.When if the diameter of spun glass is big, sting the erosion amount can choose big, thereby select to sting between 0.02 micron to 2 microns of the erosion amounts numerical value of limit on the upper side; If the diameter of spun glass hour, sting the erosion amount can choose smaller, thereby select to sting between 0.02 micron to 2 microns of the erosion amounts numerical value of limit on the lower side, if at this moment select the erosion amount of stinging bigger than normal, its result who brings is exactly that spun glass is by excessively alligatoring.The selection of stinging the erosion amount is a dynamic numerical value; The size of glass fiber diameter is maximum reference frame; Be no more than 10% glass fiber diameter size if usually sting the erosion amount, can not cause problem, cannot surpass 20% glass fiber diameter size under the extreme case; But also need be by more than 1% glass fiber diameter size, guaranteeing to obtain the better erosion effect of stinging, the ability of the bonding force between resin and the spun glass is guaranteed like this.Exceed 20% glass fiber diameter size if sting the erosion amount, at this moment the physical strength of spun glass can be in big decline, and in follow-up manufacturing process, spun glass is easy to fracture.
Treatment scheme one: this technological minimum following step that comprises: boil off → fiberglass surfacing is stung erosion alligatoring → silicon alkane coupling and is handled.Original spun glass making process has: moisture regain → warping → sizing → heald frame → last weft yarn → weave cotton cloth → boil off → grey cloth check → silicon alkane processing → inspection after construction etc.Because the grey cloth checking procedure is a checking procedure; Do not have the substantial course of processing; So in treatment scheme of the present invention, " grey cloth check " step is not write and is neglected therein, but can not think that this step of adding is a kind of innovation and obtain new patent right.The core content of this flow process is: after boil off, before silicon alkane handles, add the treatment step of " fiberglass surfacing is stung the erosion alligatoring ".For the treatment step that adds other, reason is same.As shown in fig. 1, concrete treatment step is explained as follows:
Step 100: boil off, claim to burn clean again.When glasscloth has woven completion, will to obtain clean glasscloth, make it can do further silicon coupling again and handle removing for the convenient slurry of temporarily coating of processing procedure.Because of glasscloth can not burn, but the organism that its adhering on surface can be decomposed into gas and break away from the glasscloth that so can obtain cleaning.Usually can be divided into the processing of two steps, at first be that continuous aerobic burns, and furnace temperature reaches 593～816 ℃, can burn 91～98% slurry, and then long-time low temperature batch processing; Next is that discontinuous batch of formula handled, and it is the glass cloth overline to be wrapped on the metal cylinder of porous put in the baker again, in 260 ℃～371 ℃, burns 55～100 hours, and the organic matter in the cloth is not approachingly had by further evaporating into fully.Batch formula subzero treatment method is slowly left grease and fugitive constituent in the slurry, unlikelyly causes great amount of heat energy to pour in and generates the reduction that tensile strength should be arranged.Also can adopt working method overbumt, promptly be in the thermal treatment in second step, temperature is increased to 400 ℃～650 ℃ continuous high temperatures burnt 60～100 hours, makes glasscloth stand long high temperature, thereby form situation overbumt.Through after such Temperature Treatment, in fact the crystalline structure in the glass is from the single-phase two phase structure that has been transformed into, i.e. Na
2O-B
2O
3With SiO
2Two phases have been divided the spun glass of phase, and its physical strength can descend.But under the processing of acidic substance, at the place of reacting with acidic substance, the Na in this spun glass
2O-B
2O
3Can be dissolved fall the SiO that only stays
2Structure, thus spun glass formed with coarse surface, and as strengthening acidic treatment, whole spun glass all can become the fiber yarn with microvoid structure.
Step 200: fiberglass surfacing is stung the erosion alligatoring.First method can adopt fluorine-containing material to sting erosion, and this fluorine-containing material first-selection is a gaseous phase, and its treatment effect is best.Another kind method is to adopt acidic substance to handle, carry out this processing before, need to carry out phase-splitting and handle spun glass.In treatment step to " fiberglass surfacing is stung the erosion alligatoring ", also need other relevant processing that cooperates, these are handled and can be elaborated in below " handling sub-process one " and " handling sub-process two ".
Step 300: claim silicon alkane coupling processing again.Because glass surface is very slick, other material such as water, resin etc. are not easy glass surface or fiberglass surfacing wetting well, just can not combine well between resin and the spun glass like this, thereby produce quality problem.Silane treated glass fiber surface is coated with a "coincidence" of the cortex, so that the resin in addition to the original mechanical properties, and then provide a molecular level "bond relay", drastic changes in temperature to maintain a combination of both strength , it can be called "adhesion promoter" (Adhesion? promoter).If silicon alkane processing layer can protective glass the surface, make its unlikely sticking power that loses with resin under the encirclement of moisture content, and then can keep the insulativity of dielectric material.This kind coupling agent is essentially a kind of material that blendes together (Hybrid Material), and an end has the very strong organic functional base of a kind of reagency in its molecule, and the other end then is the functional group of inorganic nature, and is middle then be the trunk of silicon alkane.The in-between unimolecular layer of this kind " coupling epithelium " has promptly formed at the film of B-stage intact man-hour.If the above silanes which compound coupling agent such as molecular structure: X-Si-R-(OCH3) 3, X is amino group, an epoxy group, and styrene.
Treatment scheme two: this technological minimum following step that comprises: boil off → open fine processing → fiberglass surfacing to sting erosion alligatoring → silicon alkane coupling processing.This flow process is compared with " treatment scheme one ", has increased to open fine the processing, and purpose is that fibrous bundle is broken up, and further increases the bonding force between resin and the spun glass.Original spun glass making process has: moisture regain → warping → sizing → heald frame → go up weft yarn → weave cotton cloth → boil off → open fine processing → grey cloth check → silicon alkane processing → inspection after construction etc.; Can certainly change, become following making processes: fine place → silicon alkane processing → inspection after construction etc. is checked → opened to moisture regain → warping → sizing → heald frame → last weft yarn → weave cotton cloth → boil off → grey cloth.Because the grey cloth checking procedure is a checking procedure; Do not have the substantial course of processing; So in treatment scheme of the present invention, " grey cloth check " step is not write and is neglected therein, but can not think that this step of adding is a kind of innovation and obtain new patent right.The core content of this flow process is: the treatment step that before silicon alkane is handled, adds " fiberglass surfacing is stung the erosion alligatoring ".For the treatment step that adds other, reason is same.As shown in Figure 2, specifically treatment step is explained as follows:
Step 100: boil off, claim to burn clean again.When glasscloth has woven completion, will to obtain clean glasscloth, make it can do further silicon coupling again and handle removing for the convenient slurry of temporarily coating of processing procedure.Because of glasscloth can not burn, but the organism that its adhering on surface can be decomposed into gas and break away from the glasscloth that so can obtain cleaning.Usually being divided into the processing of two steps, at first is that continuous aerobic burns, and furnace temperature reaches 593～816 ℃, can burn 91～98% slurry, and then long-time low temperature batch processing; Next is that discontinuous batch of formula handled, and it is the glass cloth overline to be wrapped on the metal cylinder of porous put in the baker again, in 260 ℃～371 ℃, burns 55～100 hours, and the organic matter in the cloth is not approachingly had by further evaporating into fully.Batch formula subzero treatment method is slowly left grease and fugitive constituent in the slurry, unlikelyly causes great amount of heat energy to pour in and generates the reduction that tensile strength should be arranged.Also can adopt working method overbumt, promptly be in the thermal treatment in second step, temperature is increased to 400 ℃～650 ℃ continuous high temperatures burnt 60～100 hours, makes glasscloth stand long high temperature, thereby form situation overbumt.Through after such Temperature Treatment, in fact the crystalline structure in the glass is from the single-phase two phase structure that has been transformed into, i.e. Na
2O-B
2O
3With SiO
2Two phases have been divided the spun glass of phase, and its physical strength can descend.But under the processing of acidic substance, at the place of reacting with acidic substance, the Na in this spun glass
2O-B
2O
3Can be dissolved fall the SiO that only stays
2Structure, thus spun glass formed with coarse surface, and as strengthening acidic treatment, whole spun glass all can become the fiber yarn with microvoid structure.
Step 150: open fine the processing.Open fine the processing again and claim that " water spray needle punching " (English is: Water Jet Needling) reprocess, warp thread and weft yarn are exposed in the part of cloth cover evenly open fibre, form flats.According to the depth of processing stage, can this cloth be divided into two types: only open fibre for one type; Another kind of except outside the fibre, also fluff (partly single wire fracture) through weft yarn, make cloth cover form the fine and closely woven fine hair that one deck evenly gathers, so be referred to as nylon loop.And in the simple glass cloth without the water spray processing treatment, the tight obvolvent of the single strand in warp thread and the weft yarn, through weft yarn crossover portion protuberance, quadrangle becomes the space.Open fine cloth and nylon loop because ORGANDY is released shakeouts, obviously slow down through the projection of weft yarn crossover portion, the space is inaccessible or dwindle, thereby the cloth cover smoothness improves greatly.
Step 200: fiberglass surfacing is stung the erosion alligatoring.First method can adopt fluorine-containing material to sting erosion, and this fluorine-containing material first-selection is a gaseous phase, and its treatment effect is best.Another kind method is to adopt acidic substance to handle, carry out this processing before, need to carry out phase-splitting and handle spun glass.In treatment step to " fiberglass surfacing is stung the erosion alligatoring ", also need other relevant processing that cooperates, these are handled and can be elaborated in below " handling sub-process one " and " handling sub-process two ".
Step 300: claim silicon alkane coupling processing again.Because glass surface is very slick, other material such as water, resin etc. are not easy glass surface or fiberglass surfacing wetting well, just can not combine well between resin and the spun glass like this, thereby produce quality problem.Silane treated glass fiber surface is coated with a "coincidence" of the cortex, so that the resin in addition to the original mechanical properties, and then provide a molecular level "bond relay", drastic changes in temperature to maintain a combination of both strength , it can be called "adhesion promoter" (Adhesion? promoter).If silicon alkane processing layer can protective glass the surface, make its unlikely sticking power that loses with resin under the encirclement of moisture content, and then can keep the insulativity of dielectric material.This kind coupling agent is essentially a kind of material that blendes together (Hybrid Material), and an end has the very strong organic functional base of a kind of reagency in its molecule, and the other end then is the functional group of inorganic nature, and is middle then be the trunk of silicon alkane.The in-between unimolecular layer of this kind " coupling epithelium " has promptly formed at the film of B-stage intact man-hour.Its as above-mentioned silicon alkide coupling agent molecular structure as: X-Si-R-(OCH3) 3, X is amido, epoxy radicals and styrene etc.
Need to prove; Above-mentioned two kinds of process steps can not be described out the present invention program's claim scope fully, because have the empirical people of industry, change a little; Promptly can obtain the summary of the invention inequality, but can not think that this is a kind of innovation with the flow process of foregoing description.Core content of the present invention comprises following: most crucial content is fiberglass surfacing to be stung erosion handle; This treatment step that fiberglass surfacing is stung the erosion alligatoring can be used as after the boil off treatment step, any step or substep before the silicon alkane coupling treatment step, on principle, all is feasible with using.It is the cortex in coating of fiberglass surfacing a kind of " coupling " property that silicon alkane is handled; To strengthen the bonding force between resin and the spun glass; If will be placed on silicon alkane to the processing that fiberglass surfacing is stung the erosion alligatoring is skimble-skamble after handling, and silicon alkane is handled the cortex that the back fiberglass surfacing is coated with and can be stopped that fiberglass surfacing is stung the erosion roughening treatment to carry out.Treatment step will be placed on and is about to carry out and comparatively convenient and reliable processing mode will " be stung the erosion alligatoring to fiberglass surfacing " exactly
The coupling of silicon alkane is handledBefore, " fiberglass surfacing is stung the erosion alligatoring " handles because at this moment spun glass has been made into the cloth shape, not need the cost and effort of labor just can accomplish.
Can also " fiberglass surfacing is stung the erosion alligatoring " treatment step be placed on draw out after the spun glass, any position between before the sizing treatment step, this all is feasible with using on principle.Sizing is to re-pooling arrangement through the warp, do a sizing handle (Sizing) called "pulp by", the purpose is to increase lubrication and reduce friction.If will be placed on after the sizing to the processing that fiberglass surfacing is stung the erosion alligatoring, be skimble-skamble before the boil off, the cortex that fiberglass surfacing is coated with behind the sizing can stop the carrying out that fiberglass surfacing is stung the erosion roughening treatment.The treatment step of " fiberglass surfacing being stung the erosion alligatoring " is placed on that bad part is before the sizing treatment step: at this moment spun glass also is not made into the cloth shape; At this moment spun glass is still wall scroll; " fiberglass surfacing is stung the erosion alligatoring " handles to need the manpower and the cost of labor perhaps to carry out in small batches one by one, and it is inconvenient that this operation becomes.But also there is benefit; Because be one by one or sting the erosion roughening treatment in small batches; It is splendid that the effect of handling can very reach homogeneity well; And be made into the spun glass of cloth shape because have crossover position in length and breadth and fiber yarn between stack effect, stack that thicker, position relatively leans on the lining filametntary sting erosion alligatoring effect can be poor, be in the then relatively good of the outside.So if see from this angle of treatment effect, it is reasonable selection that any position between after drawing out spun glass, before the sizing treatment step carries out that " fiberglass surfacing is stung the erosion alligatoring " handle.Way is can be after just pulling out glass fiber eaily; Glass fiber carry out " fiberglass surfacing is stung the erosion alligatoring " immediately on the path of process and handle; Can descend but accomplished its physical strength of spun glass of stinging after erosion is handled, can be in subsequent processes than being easier to fracture.
Handle sub-process one: minimumly in the treating processes of fiberglass surfacing being stung the erosion alligatoring comprise following substep: sting erosion → cleaning → oven dry.As shown in Figure 3, specifically treatment step is explained as follows:
Step 500: sting erosion.Hydrofluoric acid can dissolve a lot of all undissolvable glass of other acid (silicon-dioxide), generates the gasiform silicon tetrafluoride, in stinging the substep of erosion, exists reaction equation following: SiO
2(s)+4HF (gaseous state) → SiF
4(gaseous state)+2H
2O (liquid state).As adopt acidic substance to sting the erosion spun glass, in stinging the substep of erosion, exist reaction equation following: Na
2O+2HCl → 2NCl+H
2O, B
2O
3+ 6HCl → 2BCl
3+ 3H
2O, the material that is generated all are soluble.
Step 600: clean.Stung the fiberglass surfacing after the erosion by the gaseous state fluorine-containing material; The remaining fluorine-containing material of meeting; Need carry out clean in cleaning process, these remaining materials will be cleaned in the scavenging solution, simultaneously; Residual fluorine-containing material (like the hydrogen fluoride of gas) also can be absorbed in the scavenging solution, thereby avoids contaminate environment.This cleaning can be adopted the material with alkalescence; It can be to comprise the composition of sodium, potassium or calcium at interior material; Like materials such as yellow soda ash, sodium bicarbonate, sodium hydroxide, calcium hydroxide, Pottasium Hydroxide, salt of wormwood, saleratus or their miscellany; After having cleaned, also need adopt clear water to clean, with the unnecessary scavenging solution of flush away.As adopting acidic substance to sting the erosion spun glass, spun glass soaks in solution, can have the composition of solution, must clean up and could get into next operation.Only adopt water passable during cleaning.
Step 700: oven dry.Dry processing after cleaning, after the completion oven dry, just can enter into next treatment step.The benefit of oven dry substep is, can be so that before spun glass gets into subsequent processing, become clean, and before carrying out subsequent processing, can place for a long time.
Handle sub-process two; Minimumly in the treating processes of fiberglass surfacing being stung the erosion alligatoring comprise following substep: sting erosion → cleaning.As shown in Figure 4, specifically treatment step is explained as follows:
Step 500: sting erosion.Hydrofluoric acid can dissolve a lot of all undissolvable glass of other acid (silicon-dioxide), generates the gasiform silicon tetrafluoride, in stinging the substep of erosion, exists reaction equation following: SiO
2(solid-state)+4HF (gaseous state) → SiF
4(gaseous state)+2H
2O (liquid state).As adopt acidic substance to sting the erosion spun glass, in stinging the substep of erosion, exist reaction equation following: Na
2O+2HCl → 2NCl+H
2O, B
2O
3+ 6HCl → 2BCl
3+ 3H
2O, the material that is generated all are soluble.
Step 600: clean.Stung the fiberglass surfacing after the erosion by the gaseous state fluorine-containing material; The remaining fluorine-containing material of meeting need carry out clean, in cleaning process; These remaining materials will be cleaned in the scavenging solution; Simultaneously, residual fluorine-containing material (like the hydrogen fluoride of gas) also can be absorbed in the scavenging solution, thereby avoids contaminate environment.This cleaning can be adopted the material with alkalescence; It can be to comprise the composition of sodium, potassium or calcium at interior material; Like materials such as yellow soda ash, sodium bicarbonate, sodium hydroxide, calcium hydroxide, Pottasium Hydroxide, salt of wormwood, saleratus or their miscellany; After having cleaned, also need adopt clear water to clean, with the unnecessary scavenging solution of flush away.As adopting acidic substance to sting the erosion spun glass, spun glass soaks in solution, can have the composition of solution, must clean up and could get into next operation.Adopt water passable during cleaning.For the quantity-produced production line, subsequent processing is that silicon alkane is handled, if in fact continuous flow procedure need not to dry to get final product, can save the energy and minimizing place step like this.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, all should be regarded as belonging to protection scope of the present invention.
Claims (14)
1. the spun glass manufacturing technology of a surface coarsening; It is characterized in that; To being applied to starting material such as prepreg necessary in the electronic devices and components such as printed circuit board and IC encapsulating carrier plate in the electronic product and copper-clad plate, before these starting material of preparation, will constitute one of these raw-material essential substance: spun glass; It is coarse that the method that adopts chemical erosion is stung erosion with the surface of spun glass, to improve the bonding force between spun glass and the resin.
The method of the employing chemical erosion in the spun glass manufacturing technology of a kind of surface coarsening according to claim 1 with the surface of spun glass sting the erosion coarse; It is characterized in that; Adopt the minimum pharmaceutical chemicals that contains fluorine that fiberglass surfacing is stung erosion, thereby make that more slick originally fiberglass surfacing becomes coarse.
3. the minimum pharmaceutical chemicals that contains fluorine according to claim 2 is characterized in that, stings erosion spun glass adopted to contain minimumly in the fluorine chemistry medicine to comprise hydrofluoric composition.
4. the minimum pharmaceutical chemicals that contains fluorine according to claim 2 is characterized in that, stinging the erosion fluorine-containing pharmaceutical chemicals that spun glass adopted is minimum a kind of material that is in gaseous phase.
The method of the employing chemical erosion in the spun glass manufacturing technology of a kind of surface coarsening according to claim 1 with the surface of spun glass sting the erosion coarse; It is characterized in that; Earlier spun glass is carried out long high bake; Employing afterwards has the tart pharmaceutical chemicals fiberglass surfacing is stung erosion, thereby makes that more slick originally fiberglass surfacing becomes coarse.
6. the method for employing chemical erosion according to claim 5 is stung erosion with the surface of spun glass and is had a tart pharmaceutical chemicals in coarse, it is characterized in that, that stings erosion spun glass adopted has a minimum composition that comprises hydrogenchloride in the tart pharmaceutical chemicals.
7. the method for employing chemical erosion according to claim 5 is stung erosion with the surface of spun glass and is had a tart pharmaceutical chemicals in coarse, it is characterized in that, that stings erosion spun glass adopted has a minimum H of comprising in the tart pharmaceutical chemicals
2SO
4Composition.
8. the spun glass manufacturing technology of a kind of surface coarsening according to claim 1 is characterized in that, this technological minimum following step that comprises: boil off → fiberglass surfacing is stung erosion alligatoring → silicon alkane coupling and handled.
9. the spun glass manufacturing technology of a kind of surface coarsening according to claim 1 is characterized in that, this technological minimum following step that comprises: boil off → open fine processing → fiberglass surfacing to sting erosion alligatoring → silicon alkane coupling processing.
10. the spun glass manufacturing technology of a kind of surface coarsening according to claim 1 is characterized in that, after the boil off treatment step, before the silicon alkane coupling treatment step, fiberglass surfacing is stung the erosion roughening treatment.
11. the spun glass manufacturing technology of a kind of surface coarsening according to claim 1 is characterized in that, after drawing out spun glass, before the sizing treatment step, fiberglass surfacing is stung the erosion roughening treatment.
12. the making step in the spun glass manufacturing technology of claim 9, claim 10 and the described a kind of surface coarsening of claim 11 according to Claim 8; It is characterized in that, minimumly in the treating processes of fiberglass surfacing being stung the erosion alligatoring comprise following substep: sting erosion → cleaning → oven dry.
13. the making step in the spun glass manufacturing technology of claim 9, claim 10 and the described a kind of surface coarsening of claim 11 according to Claim 8; It is characterized in that, minimumly in the treating processes of fiberglass surfacing being stung the erosion alligatoring comprise following substep: sting erosion → cleaning.
14. the spun glass manufacturing technology of a kind of fluorine surface coarsening according to claim 1; It is characterized in that; It is coarse that the method that adopts chemical erosion is stung erosion with fiberglass surfacing, stings erosion and advance the degree of depth of fiberglass surfacing and be controlled between 1%～20% the scope that accounts for glass fiber diameter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101201324A CN102775071A (en) | 2011-05-09 | 2011-05-09 | Manufacture technology for surface-coarsened glass fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101201324A CN102775071A (en) | 2011-05-09 | 2011-05-09 | Manufacture technology for surface-coarsened glass fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102775071A true CN102775071A (en) | 2012-11-14 |
Family
ID=47120209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101201324A Pending CN102775071A (en) | 2011-05-09 | 2011-05-09 | Manufacture technology for surface-coarsened glass fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102775071A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370479A (en) * | 2014-10-16 | 2015-02-25 | 宿迁市天彩玻璃纤维有限公司 | Glass fiber surface pickling treatment device |
| CN104370475A (en) * | 2014-10-16 | 2015-02-25 | 宿迁市天彩玻璃纤维有限公司 | Glass fiber surface modifying device |
| CN104703389A (en) * | 2013-12-04 | 2015-06-10 | 罗伯特·博世有限公司 | A method for manufacturing a fiber-resin composite, especially for manufacturing a circuit board |
| CN106304690A (en) * | 2016-11-01 | 2017-01-04 | 广东生益科技股份有限公司 | A kind of method assessing reinforcing material inorganic agent and Desmear liquid medicine compatibility |
| CN109294152A (en) * | 2018-09-05 | 2019-02-01 | 浙江畅通科技有限公司 | A kind of high strength heat resistant lead-acid battery plastic housing and preparation method thereof |
| CN113136091A (en) * | 2021-03-31 | 2021-07-20 | 上海久升吸塑有限公司 | Daily tray and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066361A (en) * | 1990-05-15 | 1991-11-19 | Jonathan Scharf | Method and product for improved glass fiber reinforced and filled thermoplastic and thermosetting resin systems |
| CN1325828A (en) * | 2000-05-31 | 2001-12-12 | 化工产品开发公司 | Method for chemical roughening glass including salt solution washing process and products thereby |
| CN1426381A (en) * | 2000-04-28 | 2003-06-25 | 默克专利有限公司 | Etching pastes for inorganic surfaces |
| CN101725037A (en) * | 2009-11-27 | 2010-06-09 | 中国钢研科技集团有限公司 | Method for modifying surface of fibrous material |
-
2011
- 2011-05-09 CN CN2011101201324A patent/CN102775071A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066361A (en) * | 1990-05-15 | 1991-11-19 | Jonathan Scharf | Method and product for improved glass fiber reinforced and filled thermoplastic and thermosetting resin systems |
| CN1426381A (en) * | 2000-04-28 | 2003-06-25 | 默克专利有限公司 | Etching pastes for inorganic surfaces |
| CN1325828A (en) * | 2000-05-31 | 2001-12-12 | 化工产品开发公司 | Method for chemical roughening glass including salt solution washing process and products thereby |
| CN101725037A (en) * | 2009-11-27 | 2010-06-09 | 中国钢研科技集团有限公司 | Method for modifying surface of fibrous material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104703389A (en) * | 2013-12-04 | 2015-06-10 | 罗伯特·博世有限公司 | A method for manufacturing a fiber-resin composite, especially for manufacturing a circuit board |
| CN104370479A (en) * | 2014-10-16 | 2015-02-25 | 宿迁市天彩玻璃纤维有限公司 | Glass fiber surface pickling treatment device |
| CN104370475A (en) * | 2014-10-16 | 2015-02-25 | 宿迁市天彩玻璃纤维有限公司 | Glass fiber surface modifying device |
| CN106304690A (en) * | 2016-11-01 | 2017-01-04 | 广东生益科技股份有限公司 | A kind of method assessing reinforcing material inorganic agent and Desmear liquid medicine compatibility |
| CN106304690B (en) * | 2016-11-01 | 2019-04-30 | 广东生益科技股份有限公司 | A method of assessment reinforcing material inorganic agent and Desmear liquid medicine compatibility |
| CN109294152A (en) * | 2018-09-05 | 2019-02-01 | 浙江畅通科技有限公司 | A kind of high strength heat resistant lead-acid battery plastic housing and preparation method thereof |
| CN113136091A (en) * | 2021-03-31 | 2021-07-20 | 上海久升吸塑有限公司 | Daily tray and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102775071A (en) | Manufacture technology for surface-coarsened glass fiber | |
| JP6020764B1 (en) | Glass cloth | |
| WO2018216637A1 (en) | Glass composition, glass fiber, glass cloth, and method for manufacturing glass fiber | |
| CN100486669C (en) | Process for manufacturing high temperature filtering material of composite fibre | |
| CN106906556A (en) | A kind of Resisting fractre Strength-Glass-Fibre cloth high and its production method | |
| JP5316728B2 (en) | Glass fiber | |
| CN1193947C (en) | Method for manufacturing aluminium silicate ceramic fiber using coalgangue and its use | |
| CN112342665A (en) | Method and equipment for manufacturing high-strength high-alkali-resistance glass fiber mesh cloth | |
| WO2005080657A1 (en) | Needle felt and bag filter | |
| KR101887211B1 (en) | Temperature-resistant aluminosilicate glass fibers and method for the production thereof and use thereof | |
| JP2007262632A (en) | Method for heat cleaning glass fiber woven fabric | |
| JP2003064573A (en) | Carbon fiber tow-washing device | |
| CN102774081A (en) | Manufacture technology for high-frequency material | |
| CN109281039A (en) | The manufacturing technique method of super-thin electronic grade fiberglass cloth | |
| CN1948608A (en) | Dacron glass fiber dipped canvas and its preparation method | |
| CN101363142A (en) | Technology for covering polyphenyl thioether fabric surface with silicon coating | |
| CN115698421A (en) | Surface-treated glass cloth, prepreg, and printed wiring board | |
| CN102049160A (en) | Basalt fibre base cloth for high-temperature embroidered filter felt | |
| CN115180836A (en) | Flame-retardant glass fiber cloth and production process thereof | |
| CN114103156A (en) | Production system and method for high-elasticity-modulus high-strength glass fiber laminated board | |
| CN113209720A (en) | Preparation process of medium-alkali glass fiber filter cloth | |
| JPH03119140A (en) | Glass cloth | |
| JP2007262629A (en) | Heat cleaning method for woven glass fiber | |
| SU804587A1 (en) | Method of producing glass-fibrous materials | |
| Veit | Glass Fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| DD01 | Delivery of document by public notice |
Addressee: Dai Fang Document name: Notification that Application Deemed to be Withdrawn |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121114 |