CN1665978A - Sizing agent for glass fiber yarn and glass fiber yarn using the sizing agent - Google Patents
Sizing agent for glass fiber yarn and glass fiber yarn using the sizing agent Download PDFInfo
- Publication number
- CN1665978A CN1665978A CN038152495A CN03815249A CN1665978A CN 1665978 A CN1665978 A CN 1665978A CN 038152495 A CN038152495 A CN 038152495A CN 03815249 A CN03815249 A CN 03815249A CN 1665978 A CN1665978 A CN 1665978A
- Authority
- CN
- China
- Prior art keywords
- starch
- paraffin
- aforementioned
- vegetable oil
- mass
- 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.)
- Granted
Links
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
- C03C25/24—Coatings containing organic materials
- C03C25/255—Oils, waxes, fats or derivatives thereof
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Woven Fabrics (AREA)
Abstract
A collecting agent for a glass fiber yarn prepared by twisting strands each formed by collecting 50 to 800 glass filaments having an average diameter of 5 to 9 mum, which comprises an etherificated starch having an amylose content of 50 % or less, an etherificated high-amylose starch having an amylose content of 50 % or more, a vegetable oil, a paraffin, an emulsifier for the vegetable oil and an emulsifier for the paraffin, wherein the etherificated starch and the etherificated high-amylose starch are contained in a mass ratio of 25 to 75 : 75 to 25, and the emulsifier for the vegetable oil is contained in an amount of 5 to 12 parts by mass relative to 100 parts by mass of the total starch; and a glass fiber yarn using the collective agent. The glass fiber yarn is used as a wrap and/or a weft of a glass cloth, is free from the formation of fluffs during air-jet weaving and is excellent in heat cleaning property and the resistance to the fall of a powder.
Description
Technical field
Glass fiber yarn in the glass cloth that the present invention relates to be applied to use, its boundling method, used collecting agent and glass cloth etc. mainly as the baseplate material of printed wiring board etc.
Background technology
Glass fiber yarn be with hundreds of be that several microns glass monofilament becomes tow with the collecting agent boundling to 1,000 plurality of fibers diameters, again with this tow twisting gained.Then, this glass fiber yarn makes glass cloth by weaving process, and is immersed in this glass cloth by resin is contained, and can be used as the uses such as reinforcing material of fibre reinforced plastics (FRP) goods.
In recent years, as the purposes of glass cloth, be suitable for and gaze at for the baseplate material of printed wiring board particularly is subjected to the people.In the manufacturing process of printed wiring board, resin such as epoxy is contained immerse glass cloth to form prepreg, the more further Copper Foil of laminated thin etc. and making.Therefore, in order not damage Copper Foil, require the defectives such as lousiness of glass cloth surface to lack as best one can.
On the other hand, in the weaving process of above-mentioned glass cloth, will be wound as bobbin, carry out weaving between warp thread and weft yarn by air-jet loom etc. then the glass fiber yarn that above-mentioned tow adopts ring doubling frame twisting to make.
At this, for the warp thread and the weft yarn of glass cloth, generally its to require performance be different.Promptly, before weaving process, require to have the operation that is called warping process (warping) for warp thread.In order to prevent the generation of above-mentioned lousiness, not only be necessary to improve the convergence of glass fiber yarn, also to the maneuverability in the warping process with prevent that from there is requirement dust whereabouts etc.
With respect to this, weft yarn because be that laterally to enter be feature to carry by air, so except by giving convergence prevents that lousiness from producing, also be necessary to have the fugacity of being carried by air easily, therefore requires the fibre of opening of appropriateness in air-jet loom.
Maneuverability when the convergence of glass fiber yarn, warping, dust fall prevents, the fugacity when going into latitude etc. can be formed by the collecting agent when the glass monofilament boundling is tow and adjust.But as mentioned above, because warp thread is different with the desired performance of weft yarn, the past normally adopts different collecting agents to satisfy above desired performance respectively to warp thread and weft yarn.
In addition, the glass cloth of baseplate material that is applied to above-mentioned printed wiring board will carry out the heat that is called as heating de-oiling operation that collecting agent and secondary filler are removed by oxidation, thermal decomposition etc. is cleaned after weaving.Therefore, for making not remaining organic analyte and carbide on the glass cloth after this heat is cleaned, also require glass cloth to have good hot cleaning.
As satisfy the above-mentioned multiple collecting agent that requires performance, for example mixture of two kinds of chemical starches that the employing viscosity (molecular weight) that is disclosed is different in Japanese patent laid-open 10-72243 communique.Promptly put down in writing as both reducing dust whereabouts and fluffing, can obtain the chemical starch of the glass fiber sizing agent of the rigid yarn of appropriateness again, it has the chemical starch of 1～5CPS viscosity and 95～5wt% by 5～95wt% and have the glass fibre collecting agent chemical starch that the chemical starch of 6～50CPS viscosity is formed in 60 ℃, 5% aqueous solution in 60 ℃, 5% aqueous solution.
As mentioned above, because warp thread is different with the desired performance of weft yarn, the past, both collecting agents can not be unified, and therefore, warp thread separates manufacturing with weft yarn, in engineering complexity, manufacturing and administration fee time, also had the problem of cost increase like this.
In addition, in the collecting agent of above-mentioned Japanese patent laid-open 10-72243 communique, although can reduce dust whereabouts and fluffing by limiting starch, but and therefore the combination of finish composition or emulsifying agent exists the problem that can not satisfy warp thread, weft yarn, the desired performance of glass cloth simultaneously because do not limit.The performance that warp thread is required is the maneuverability when guaranteeing necessary convergence, warping process and prevents that dust from falling; The performance that weft yarn is required is the fugacity when guaranteeing necessary convergence, air-jet weaving; To the glass cloth requirement is hot cleaning.
Therefore, the object of the present invention is to provide glass fiber yarn collecting agent, boundling method and glass fiber yarn etc.This collecting agent can be used for the warp thread and the weft yarn of the used glass cloth of printed wiring board.As warp thread, convergence is good, can prevent that lousiness from producing, and can obtain the flatness of stable maneuverability and appropriateness, and prevent dust whereabouts property excellence in warping process; As weft yarn, convergence is good, can prevent that lousiness from producing, and when air-jet loom is made the fugacity excellence.
The announcement of invention
In order to achieve the above object, present inventors are through further investigation, and the result obtains following discovery: (1) is by two kinds of starch that amylose content is different and be used as starch, can improve convergence, suppress lousiness and produce, and improve hot cleaning.(2) in addition, by with the combination of vegetable oil and paraffin as finish, both improved convergence, also make as weft yarn open fibre, maneuverability excellence during as the warp thread warping.(3) proportioning that reaches regulation by the emulsification dosage that makes vegetable oil can suppress the generation of lousiness.The result of above-mentioned research has found the present invention can satisfy above-mentioned all in the past collecting agents that requires performance evenly.
So it is feature that the present invention has following main points:
1. glass fiber yarn collecting agent, it is that to be used for 50～800 average root diameters be that the glass monofilament boundling of 5～9 μ m is the collecting agent of boundling of twisting the aforementioned tow of the glass fiber yarn that warp thread and/or the weft yarn as the glass cloth that form use behind the tow again, the feature of this collecting agent is, aforementioned collecting agent contains starch at least, vegetable oil, paraffin, the emulsifying agent of aforementioned vegetable oil and the emulsifying agent of aforementioned paraffin, aforementioned starch comprise amylose content less than 50% etherification starch and amylose content more than or equal to 50% etherificate high amylose starches (Ha イ ア ミ ロ-ス), the proportioning of aforementioned etherification starch and aforementioned etherificate high amylose starches counts 25～75 with parts by mass: 75～25, and be 5～12 parts by mass with respect to the content of the emulsifying agent of the aforementioned vegetable oil of aforementioned starch 100 parts by mass.
2. the collecting agent of above-mentioned 1 record, wherein, aforementioned paraffin comprises solid paraffin, and the fusing point of described solid paraffin is 45～53 ℃.
3. the collecting agent of above-mentioned 1 or 2 records, wherein, aforementioned paraffin comprises solid paraffin and atoleine, and the proportioning of described solid paraffin and described atoleine counts 10～50 with parts by mass: 90～50.
4. glass fiber yarn, this yarn has adhered to the collecting agent of each record in above-mentioned 1～3 and has formed.
5. the boundling method of glass fiber yarn, it is to be that the glass monofilament boundling of 5～9 μ m is the boundling method of twisting the aforementioned tow of the glass fiber yarn that warp thread and/or the weft yarn as the glass cloth that form use behind the tow again with 50～800 average root diameters, the feature of this method is, aforementioned collecting agent contains starch at least, vegetable oil, paraffin, the emulsifying agent of aforementioned vegetable oil and the emulsifying agent of aforementioned paraffin, aforementioned starch comprise amylose content less than 50% etherification starch and amylose content more than or equal to 50% etherificate high amylose starches, the proportioning of aforementioned etherification starch and aforementioned etherificate high amylose starches counts 25～75 with parts by mass: 75～25, and the proportioning of aforementioned vegetable oil and paraffin counts 30～70 with parts by mass: 70～30, and be 5～12 parts by mass with respect to the content of the emulsifying agent of the aforementioned vegetable oil of aforementioned starch 100 parts by mass.
6. glass cloth, it is to be that the glass monofilament of 5～9 μ m is to twist the glass cloth that the glass fiber yarn that forms uses as the warp thread and/or the weft yarn of glass cloth behind the tow again by the collecting agent boundling with 50～800 average root diameters, the feature of this glass cloth is, aforementioned collecting agent contains starch at least, vegetable oil, paraffin, the emulsifying agent of aforementioned vegetable oil and the emulsifying agent of aforementioned paraffin, aforementioned starch comprise amylose content less than 50% etherification starch and amylose content more than or equal to 50% etherificate high amylose starches, the proportioning of aforementioned etherification starch and aforementioned etherificate high amylose starches counts 25～75 with parts by mass: 75～25, and the proportioning of aforementioned vegetable oil and paraffin counts 30～70 with parts by mass: 70～30, and the content of the emulsifying agent of aforementioned vegetable oil is 5～12 parts by mass.
7. the baseplate material of printed wiring board, the feature of this material are to have used the glass cloth of above-mentioned 6 records.
The best mode that carries out an invention
Below, the present invention is specifically described.
Glass fiber yarn of the present invention contains the emulsifiable concentrate of starch, vegetable oil, paraffin, above-mentioned vegetable oil and the emulsifying agent of above-mentioned paraffin at least with collecting agent.This starch comprise amylose content less than 50%, preferably 15～40% etherification starch (being designated hereinafter simply as etherification starch) and amylose content more than or equal to 50%, preferably 60～85% etherificate high amylose starches (being designated hereinafter simply as the etherificate high amylose starches).
At first, describe being used for starch of the present invention, starch also forms agent cover glass fiber as tunicle and avoids the bending in the operation, the influence of friction when making the monofilament boundling.In addition, starch is compared with finish, and is residual easily after hot matting, so the selection of this starch has influence on hot cleaning.
Again, in the present invention, conventional etherification starch and etherificate high amylose starches are also with being a big feature.
Among the present invention, can improve by film-strength and convergence, but when using separately, then make hot cleaning and the property decline of dust whereabouts by using the etherificate high amylose starches.Therefore among the present invention and used etherification starch, can satisfy the requirement that prevents lousiness generation, hot cleaning, dust whereabouts property simultaneously by the raising of convergence like this.
Kind to starch material is not particularly limited, and cornstarch, tapioca, wheaten starch, sweet potato starch, farina etc. all can use, but the impurity beyond starch is few, particle diameter is little, the viewpoint of easy acquisition, preferably uses cornstarch.
Aforementioned starch adopts the etherification starch of ether modification.Can exemplify carboxy methylation, hydroxyalkylation, alkylation, benzylization, CATION etherificate etc. as etherificate.Wherein best is hydroxyalkylation.Since adopt aforementioned etherification starch, because the gelatinization initial temperature reduces, thus easily gelatinization, and can make solution-stabilizedization.In addition, when heat is cleaned, can also make by the starch of membranization and can remove with comparalive ease.
Such hydroxyalkylation can make for example oxirane, expoxy propane, 1, and 2-epoxy butane etc. acts on above-mentioned starch and obtains.
Feature of the present invention is that the proportioning of above-mentioned etherification starch and etherificate high amylose starches counts 25～75 with parts by mass: 75～25, preferably 40～60: 60～40.The generation of lousiness can be suppressed like this, and the collecting agent of hot cleaning, dust whereabouts property excellence can be obtained.If corresponding to the proportioning of whole etherificate high amylose starchess of starch less than 25 quality %, then convergence poor, be easy to generate lousiness, so undesirable.Otherwise if surpass 75 quality %, then the dust whereabouts is many, and hot cleaning is also poor, so also undesirable.
Then, describe being used for finish of the present invention.Using the main purpose of finish is to give tow with lubricity.
Feature of the present invention is also to use vegetable oil and paraffin as finish.Only use vegetable oil, then, then can give flatness, and give out fibre by this, can improve the fugacity of air-jet loom because the lubricity deficiency so fugacity is also bad when producing lousiness, makes wherein to comprise paraffin.But, if having only paraffin,, open fine surplus on the contrary although fugacity improves, increased the generation of lousiness, so must and use both.
Vegetable oil is not particularly limited, can exemplifies coconut oil, palm oil, palm-kernel oil, corn oil, cottonseed wet goods.In addition, vegetable oil can be undersaturated, also can be the saturated vegetable oil that adds behind the water.They can separately or mix more than 2 kinds and use.Again, among the present invention, vegetable oil can also use the vegetable and animals oils of animal oil such as lard and this vegetable oil and usefulness.When using vegetable and animals oils, following plant oil mass refers to the animals and plants oil mass.
As paraffin, can be used alone or as a mixture solid paraffin and atoleine.The fusing point of general used solid paraffin is 45～70 ℃, better is 45～53 ℃, is more preferably 45～50 ℃.Maneuverability in the time of can making warping like this is good, can suppress the generation of lousiness.If above-mentioned value surpasses 53 ℃, then the maneuverability during warping is poor, undesirable.
Be more preferably and except above-mentioned solid paraffin, also contain atoleine.Maneuverability during like this because of warping is better, so can suppress the generation of lousiness.In this case, solid paraffin: the proportioning of atoleine better is 10～50: 90～50 in parts by mass, is more preferably 20～40: 80～60.Corresponding to paraffin integral body, if the content of atoleine is less than 50 quality %, maneuverability during then because of the warp thread warping is insufficient, be easy to generate lousiness, so undesirable, if but surpass 90 quality %, then the weft yarn in the air-jet loom open fine superfluous, increased the generation of lousiness, so also undesirable.
Again, the content of the finish of forming as vegetable oil and paraffin, with respect to aforementioned starch 100 parts by mass, the content of aforementioned paraffin and aforementioned vegetable oil better is 10～40 parts by mass, is more preferably 20～35 parts by mass as finish integral body.If the content of aforementioned paraffin and aforementioned vegetable oil is less than 10 parts by mass, the fugacity when then weaving is poor, thus undesirable, if but surpass 40 parts by mass, then because the tunicle of collecting agent to form property poor, so be easy to generate lousiness during warping, also undesirable.
It is 30～70 that the proportioning of paraffin and vegetable oil is haggled over parts by mass: 70～30, be more preferably 40～60: 60～40.According to this proportioning, paraffin has been given flatness, has suppressed excessive lubricating with vegetable oil again simultaneously, can prevent the generation of lousiness, has obtained all excellent collecting agent of convergence and maneuverability both sides.If paraffin less than 30 parts by mass %, then can not obtain sufficient lubricity to the proportioning of finish, the maneuverability during warping descends, and the fugacity when weaving also descends, so undesirable.Otherwise, if surpass 70 quality %,, to open fine superfluously although the fugacity when weaving improves, lousiness is easy to generate, and is therefore also undesirable.
In collecting agent of the present invention, also contain the emulsifying agent of above-mentioned paraffin and the emulsifying agent of vegetable oil again.
As the emulsifying agent of paraffin, be preferably and contain the emulsifying agent that ether is emulsifying agent at least.Be that the combination of emulsifying agent has formed paraffin emulsion especially by paraffin and ether like this, can improve the fibre of opening of glass fiber yarn.
As above-mentioned ether is emulsifying agent, better be the ethylene oxide adduct of higher alcohol, specifically comprise polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether as the nonionic Surfactant, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene octadecyl ether, polyoxyl 10 oleyl ether; Phenylate type emulsifying agents such as polyoxyethylene nonyl phenylate, polyoxyethylene octyl group phenylate.
In addition, above-mentioned ether is that the content of emulsifying agent is the total amount of emulsifying agent with respect to paraffin and ether, better is 10～40 quality %, and good especially is 10～25 quality %.Can suppress surplus like this and open generation fine and lousiness.If ether be the content of emulsifying agent less than 10 quality %, it is insufficient then to open fibre; If surpass 40 quality %, then open fine surplus, increased the generation of lousiness.
Again, as the emulsifying agent of aforementioned paraffin, preferably also containing ester is emulsifying agent.Open fibre like this and can further improve, even a small amount of interpolation also can make the fugacity of air-jet loom improve.
As ester is emulsifying agent, for example can use polyoxyethylene mono alkyl esters such as Vinlub 73, polyoxyl 40 stearate, Aceonon 300 MO; Sorbitan esters such as Span-20, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, Span-83, sorbitan trioleate; Fatty glycerides such as Unigly GO 102S, polyglycereol laurate, polyglycereol stearate.Wherein use fatty glyceride better.
Again, can to use mentioned emulsifier also can use separately multiple for the emulsifying agent of paraffin.
On the other hand, as the emulsifying agent of vegetable oil, can use known in the past nonionic surface active agent, can use ester system, ether system, ether-ether is in the emulsifying agent etc. any.Ester system, ether are that emulsifying agent can use the emulsifying agent same with the emulsifying agent of above-mentioned paraffin.As ether-ether is emulsifying agent, specifically can exemplify sorbitan ester ether type emulsifying agents such as Tween-20, Tween-40, polyoxyethylene sorbitol acid anhydride single-hard ester acid ester, Tween-81 etc.
Wherein, ester system or ether-ether are that emulsifying agent is opened fibre because can obtain the appropriateness of glass fiber yarn, so better, wherein good especially is polyoxyethylene mono alkyl ester, sorbitan ester or sorbitan ester ether type.
Among the present invention, the emulsifier content of this vegetable oil is 5～12 parts by mass with respect to starch 100 parts by mass, better is 6～9 parts by mass.Can further improve the generation of convergence, inhibition lousiness like this.With respect to starch 100 parts by mass, if the content of the emulsifying agent of vegetable oil less than 5 parts by mass, emulsified state instability then, collecting agent can not be attached to tow fully, therefore is easy to generate lousiness; If surpass 12 parts by mass, then open fine superfluously, be easy to generate lousiness in warping or when weaving.
Again, can to use mentioned emulsifier also can use separately multiple for the emulsifying agent of vegetable oil.
Except mentioned component, also can comprise other composition in the collecting agent of the present invention.These compositions can exemplify cationic lubricant, mould inhibitor, also can exemplify silane coupling agent and other various additives.
As the manufacture method of above-mentioned collecting agent, according to known method in the past, can be by will after finish and the emulsifier being decentralized medium and the emulsion of emulsifying adds in the starch with water, be mixed into other composition again and make.
The present invention in the emulsification process of finish and emulsifying agent, though also can with vegetable oil and paraffin and to contain ether at least be that the emulsifying agent of emulsifying agent is mixed together back emulsification, preferably vegetable oil with mix again after paraffin reaches emulsified state respectively separately.
Like this with vegetable oil, paraffin, to contain ether at least be that the situation of the emulsifying agent emulsification of emulsifying agent is compared, because paraffin is more stable with the emulsified state that contains emulsifying agent that ether is emulsifying agent and vegetable oil and emulsifying agent at least, so when making out fibre good, can suppress the generation of lousiness effectively.
Below, the glass fiber yarn of the present invention and the glass cloth that obtain using above-mentioned collecting agent describe.
The glass fiber yarn collecting agent of the invention described above be with 50～800, better be that 100～400 average root diameters are 5～9 μ m, adhere to as collecting agent when better the glass monofilament boundling of 6～8 μ m obtains tow.Tow with above-mentioned fiber diameter, boundling number can exemplify the tow that number is 2～140 spies (tex).
Give the method for glass fibre, the method that can adopt roller dispenser etc. to be coated with collecting agent.The quality of the glass fiber strand after the adhesion amount of collecting agent adheres to collecting agent is a standard, is preferably 0.3～2 quality % admittedly form component, and good especially is 0.5～1.5 quality %.Again, though adhere to collecting agent any time of time after fibration can, in order to adhere to effectively, preferably after fibration, adhere to immediately.
The tow that has adhered to above-mentioned collecting agent is further twisted the formation glass fiber yarn, as the warp thread and/or the weft yarn use of glass cloth.At this, twist thread and to use known in the past ring doubling frame.The twist also is not particularly limited, and better is 0.1～2.0 time/25mm, and good especially is 0.5～1.0 time/25mm.
The kind of the representative glass fiber yarn of Huo Deing can exemplify the Glass yarn of ECE225 among the JIS-R3413 (the per 1 pound of yardage of 225 expressions 1/100) like this.
When above-mentioned glass fiber yarn uses as the warp thread of glass cloth, before supplying with loom, to carry out warping process.In warping process, according to the radical of Fabric Design, in proper order, length, density, fabric width etc., carry out the operation of putting on the shelf of bobbin cradle, this operation is in order to make one one glass fiber yarn draw neat doubling from a plurality of bobbins of the warp thread of having reeled.Then, these multi-filaments on the bobbin are pulled out be arranged in parallel, Yi Bian give same tension force, Yi Bian be wound up on the axle of warping footpath.Necessary warp thread when thus, being ready to weave.Beaming method is not particularly limited, also can the part warping.
Owing to adopt the convergence excellence of the glass fiber yarn of collecting agent of the present invention, therefore the lousiness that produces in warping process is few.And, because running tension is stable, so can obtain the maneuverability of excellence during warping.In addition, the dust that falls during warping is also few.
Then, will as the warp beam of warp thread with load onto loom as the bobbin of weft yarn, utilize weaving process to make glass cloth.As loom,, preferably adopt air-jet loom from weaving at a high speed.And, because the fibre of opening that adopts the weft yarn of collecting agent of the present invention to have appropriateness, thus when air-jet loom laterally enters the fugacity excellence, can realize that low-pressure air carries.
As above-mentioned weaving condition, can use known in the past condition, it is not particularly limited.In addition, fabric construction also is not particularly limited, when for example using, adopts plain weave structure for well as the baseplate material of printed wiring board.
Knit like this glass cloth defectives such as surperficial lousiness seldom, mainly applicable to the purposes of printed wiring board.
Embodiment
Below, the present invention will be described in more detail by embodiment, but the present invention is not limited in these embodiment.In addition, in following embodiment and comparative example, the proportional quantity of each composition is the percentage of the collecting agent that contains medium of final gained when totally being 100 quality %, promptly shown in following table 1, with the fraction values record in the collecting agent main assembly that comprises aqueous medium of final gained.
Embodiment 1
The modulation of＜starch gelatinization liquid 〉
With 2.2 quality % (as mentioned above, it is the fraction values in the collecting agent main assembly that comprises aqueous medium of final gained, below identical) be dispersed in the water as the hydroxypropyl cornstarch (amylose content 30%) of etherification starch hydroxypropyl amylomaize (amylose content 70～75%) with 2.2 quality %, heating then, in 95 ℃ of following gelatinizations 30 minutes, obtain dextrin.
The modulation of＜vegetable oil (vegetable and animals oils) emulsion 〉
The vegetable and animals oils of being made up of palm oil lard corn oil of 0.65 quality % and 0.21 quality % dissolved as polyoxyethylene sorbitol four oleates of emulsifying agent and 0.11 quality % polyethylene glycol monooleate mix, carry out emulsification with 80 ℃ hot water, obtain vegetable oil milkiness liquid.
The modulation of＜paraffin emulsion 〉
The solid paraffin that with 0.55 quality % fusing point is 46 ℃ dissolves and mixes as polyoxyethylene octadecyl ether, the 0.04 quality % polyglycereol stearate of emulsifying agent with 0.10 quality %, advances emulsification with 80 ℃ hot water, obtains paraffin emulsion.
The modulation of＜other adding ingredient 〉
Cationic lubricant and 0.01 quality % mould inhibitor that 0.2 quality % is made up of tetren (TEPA) and stearic acid condensation product acetate are dispersed in the hot water together.
The modulation of＜collecting agent 〉
Above-mentioned starch gelatinization liquid, vegetable oil milkiness liquid, paraffin emulsion, cationic lubricant and mould inhibitor are mixed together, add warm water, obtain the collecting agent of the embodiment 1 shown in the table 1 (dividing) Gu form.
Embodiment 2
Except in the modulation of paraffin emulsion, adopting 0.18 quality % fusing point as paraffin is outside 46 ℃ the solid paraffin and 0.36 quality % atoleine, other modulator approach with embodiment 1 is identical, obtains the collecting agent of the embodiment 2 shown in the table 1 (dividing Gu form).
Embodiment 3
Except in the modulation of paraffin emulsion, adopting 0.55 quality % fusing point as paraffin is that other modulator approach with embodiment 1 is identical outside 54 ℃ the solid paraffin, obtains the collecting agent of the embodiment 3 shown in the table 1 (solid form minute).
Comparative example 1
Except in the modulation of starch gelatinization liquid, adopt outside the 4.4 quality % hydroxypropyl amylomaizes as starch, other modulator approach with embodiment 1 is identical, obtains the collecting agent of the comparative example 1 shown in the table 1 (dividing Gu form).
Comparative example 2
Except in the modulation of starch gelatinization liquid, adopt outside the 4.4 quality % hydroxypropyl cornstarchs as starch, other modulator approach with embodiment 1 is identical, obtains the collecting agent of the comparative example 2 shown in the table 1 (dividing Gu form).
Comparative example 3
Except in the modulation of the emulsion of vegetable oil, adopt outside 0.11 quality % polyoxyethylene sorbitol four oleates and the 0.06 quality % polyethylene glycol monooleate as emulsifying agent, other modulator approach with embodiment 1 is identical, obtains the collecting agent of the comparative example 3 shown in the table 1 (dividing Gu form).
Comparative example 4
Except in the modulation of the emulsion of vegetable oil, adopt outside 0.42 quality % polyoxyethylene sorbitol four oleates and the 0.22 quality % polyethylene glycol monooleate as emulsifying agent, other modulator approach with embodiment 1 is identical, obtains the collecting agent of the comparative example 4 shown in the table 1 (dividing Gu form).
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Cornstarch (amylose content 70-75%) | ??2.2 | ??2.2 | ??2.2 | ??4.4 | ??2.2 | ??4.4 | |
| Cornstarch (amylose content 30%) | ??2.2 | ??2.2 | ??2.2 | ??4.4 | ??2.2 | ||
| Vegetable oil | ??0.65 | ??0.65 | ??0.65 | ??0.65 | ??0.65 | ??0.65 | ??0.65 |
| Polyoxyethylene sorbitol four oleates | ??0.21 | ??0.21 | ??0.21 | ??0.21 | ??0.21 | ??0.11 | ??0.42 |
| Polyethylene glycol monooleate | ??0.11 | ??0.11 | ??0.11 | ??0.11 | ??0.11 | ??0.06 | ??0.22 |
| Solid paraffin (54 ℃ of fusing points) | ??0.55 | ||||||
| Solid paraffin (46 ℃ of fusing points) | ??0.55 | ??0.18 | ??0.55 | ??0.55 | ??0.55 | ??0.55 | |
| Atoleine | ??0.36 | ||||||
| Ether is emulsifying agent | ??0.10 | ??0.10 | ??0.10 | ??0.10 | ??0.10 | ??0.10 | ??0.10 |
| The polyglycereol stearate | ??0.04 | ??0.04 | ??0.04 | ??0.04 | ??0.04 | ??0.04 | ??0.04 |
| Cationic lubricant | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 | ??0.2 |
| Mould inhibitor | ??0.01 | ??0.01 | ??0.01 | ??0.01 | ??0.01 | ??0.01 | ??0.01 |
| Divide mixture Gu form | ??6.3 | ??6.2 | ??6.3 | ??6.3 | ??6.3 | ??6.1 | ??6.6 |
| Water | ??93.7 | ??93.8 | ??93.7 | ??93.7 | ??93.7 | ??93.9 | ??93.4 |
The test example
Adopt the collecting agent of embodiment 1～3 and comparative example 1～4 to make glass cloth, detect lousiness radical, dust whereabouts situation and the hot cleaning of glass cloth surface.
In addition, glass fiber yarn and glass cloth are by following condition manufacturing.
At first, with 200 average root diameters is that the glass monofilament boundling of 7 μ m is made tow, above-mentioned various collecting agents are adhered to after fibration immediately, with the quality of having adhered to the glass fiber strand behind the collecting agent is standard, makes the solid formation component of the collecting agent that is attached to this tow reach 1.0 quality %.
Then, adopt ring spinner that this tow is twisted thread, obtain the glass fiber yarn of ECE225 1/0 1.0Z in JIS-R3413.
At last, with this glass fiber yarn as warp thread and weft yarn, adopt air-jet loom knit glass cloth.
Again, lousiness radical, per 1 meter for weft yarn
2The lousiness radical from weft yarn of glass cloth is with the naked eye observed respectively and is measured; Lousiness radical for warp thread per 800 warp thread in a warping footpath axle adopts the lousiness monitoring machine to measure.
Dust falls, and the whereabouts of collecting agent amount is estimated by visual in warping process.Be divided into ◎: excellent; Zero: good; *: differ from 3 class and estimate.
Hot cleaning as quick evaluation, heats up collecting agent on the differential thermobalance with 20 ℃/minute speed, measure the survival rate when being warmed up to 300 ℃ and judge that survival rate is designated as ◎ below 60%; 60～70% are designated as zero; Be designated as more than 70% *.
The said determination result gathered be shown in table 2.
Table 2
| The lousiness radical | Dust falls | Hot cleaning | |||
| Warp thread | Weft yarn | Judge | Survival rate % | ||
| Embodiment 1 | ????4 | ????1.1 | ????○ | ????○ | ????66 |
| Embodiment 2 | ????2 | ????0.7 | ????○ | ????○ | ????64 |
| Embodiment 3 | ????6 | ????1.1 | ????○ | ????○ | ????64 |
| Comparative example 1 | ????3 | ????0.5 | ????× | ????× | ????74 |
| Comparative example 2 | ????11 | ????3.2 | ????◎ | ????◎ | ????57 |
| Comparative example 3 | ????13 | ????1.8 | ????○ | ????○ | ????65 |
| Comparative example 4 | ????10 | ????1.5 | ????○ | ????○ | ????66 |
Can find out that from the result of table 2 the lousiness radical of embodiments of the invention 1～3, warp thread are 2～6, weft yarn is 0.7～1.1, and is all less; Dust falls, hot cleaning is also all good.
In addition, paraffin melting point is that 46 ℃ embodiment 1 is that the lousiness radical of 54 ℃ embodiment 3 lacks than paraffin melting point.And the embodiment 2 that adopts solid paraffin and atoleine and usefulness as paraffin further lacks than the lousiness radical of the embodiment 1 of independent employing solid paraffin.
With respect to this, only adopt the comparative example 1 of hydroxypropyl amylomaize as starch, although the lousiness radical is less, dust falls and hot cleaning significantly descends.And only adopt the comparative example 2 of hydroxypropyl cornstarch as starch, though that dust falls is fine with hot cleaning, the lousiness radical increases to some extent.
In addition, less than the comparative example 3 of the lower limit of prescribed limit of the present invention and the comparative example 4 that surpasses higher limit, because of the convergence deficiency, the lousiness radical of warp thread and weft yarn all increases to some extent with respect to the proportional quantity of the emulsifying agent of the vegetable oil of starch.
The possibility of utilizing on the industry
As the warp thread of glass cloth and/or the glass fiber yarn of weft yarn use, by adopting collecting agent of the present invention, the lousiness in the time of can effectively preventing air-jet loom weaving produces. And dust falls, hot cleaning is also excellent. Therefore, used the glass fiber yarn of this collecting agent, applicable to used glass cloth in printed wiring board etc.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP190600/2002 | 2002-06-28 | ||
| JP2002190600A JP2004035280A (en) | 2002-06-28 | 2002-06-28 | Sizing agent for glass fiber yarn and glass fiber yarn using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1665978A true CN1665978A (en) | 2005-09-07 |
| CN100478516C CN100478516C (en) | 2009-04-15 |
Family
ID=29996892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038152495A Expired - Fee Related CN100478516C (en) | 2002-06-28 | 2003-06-26 | Collecting agent for glass fiber yarn and glass fiber yarn using the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2004035280A (en) |
| CN (1) | CN100478516C (en) |
| WO (1) | WO2004003282A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249555A (en) * | 2011-04-25 | 2011-11-23 | 重庆国际复合材料有限公司 | Electronic yarn sizing agent and preparation method thereof |
| CN102503185A (en) * | 2011-11-23 | 2012-06-20 | 安徽丹凤电子材料股份有限公司 | Glass fiber soaking agent and preparation method thereof |
| CN103708741A (en) * | 2013-12-19 | 2014-04-09 | 清远忠信世纪玻纤有限公司 | Starch-type textile impregnating compound and preparation method thereof |
| CN104328579A (en) * | 2014-08-27 | 2015-02-04 | 安徽丹凤电子材料股份有限公司 | Preparation process of glass fiber cloth |
| CN106966611A (en) * | 2017-04-12 | 2017-07-21 | 广东志造生物科技有限公司 | A kind of D450 electronic yarn sizing agents and preparation method thereof |
| CN112973280A (en) * | 2021-02-05 | 2021-06-18 | 江苏九鼎新材料股份有限公司 | Method for manufacturing expanded glass fiber mesh cloth |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5405871B2 (en) * | 2009-03-27 | 2014-02-05 | 日東紡績株式会社 | Glass fiber sizing agent and glass fiber bundle |
| CN109778389A (en) * | 2018-12-18 | 2019-05-21 | 中材科技股份有限公司 | A kind of glass fabric and preparation method thereof |
| CN112374769A (en) * | 2020-04-20 | 2021-02-19 | 河南光远新材料股份有限公司 | Impregnating compound for glass fiber spun yarn and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07197380A (en) * | 1993-12-28 | 1995-08-01 | Unitika Ltd | Warp-sizing agent for glass woven fabric and heat-cleaning method for glass woven fabric sized therewith |
| JP4224869B2 (en) * | 1997-10-03 | 2009-02-18 | 日東紡績株式会社 | Glass fiber fabric |
| JP4016082B2 (en) * | 1998-03-10 | 2007-12-05 | 日澱化學株式会社 | Modified starch for glass fiber sizing agent, sizing agent, and glass fiber to which it is attached |
| JP4245238B2 (en) * | 1999-09-07 | 2009-03-25 | 株式会社Ａｄｅｋａ | Glass fiber sizing agent |
| JP2001240432A (en) * | 2000-02-29 | 2001-09-04 | Nippon Sheet Glass Co Ltd | Binder for glass fiber and glass fiber having the binder adhered thereon |
| JP2001271268A (en) * | 2000-03-21 | 2001-10-02 | Nippon Sheet Glass Co Ltd | Glass filament sizing agent and the resultant glass filament yarn |
| JP4449198B2 (en) * | 2000-09-28 | 2010-04-14 | 日東紡績株式会社 | Glass fiber sizing agent, glass fiber coated with the same, and glass fiber wound body thereof |
-
2002
- 2002-06-28 JP JP2002190600A patent/JP2004035280A/en active Pending
-
2003
- 2003-06-26 CN CNB038152495A patent/CN100478516C/en not_active Expired - Fee Related
- 2003-06-26 WO PCT/JP2003/008137 patent/WO2004003282A1/en active Application Filing
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249555A (en) * | 2011-04-25 | 2011-11-23 | 重庆国际复合材料有限公司 | Electronic yarn sizing agent and preparation method thereof |
| CN102503185A (en) * | 2011-11-23 | 2012-06-20 | 安徽丹凤电子材料股份有限公司 | Glass fiber soaking agent and preparation method thereof |
| CN102503185B (en) * | 2011-11-23 | 2013-11-27 | 安徽丹凤电子材料股份有限公司 | Glass fiber soaking agent and preparation method thereof |
| CN103708741A (en) * | 2013-12-19 | 2014-04-09 | 清远忠信世纪玻纤有限公司 | Starch-type textile impregnating compound and preparation method thereof |
| CN103708741B (en) * | 2013-12-19 | 2017-02-01 | 清远忠信世纪玻纤有限公司 | Starch-type textile impregnating compound and preparation method thereof |
| CN104328579A (en) * | 2014-08-27 | 2015-02-04 | 安徽丹凤电子材料股份有限公司 | Preparation process of glass fiber cloth |
| CN106966611A (en) * | 2017-04-12 | 2017-07-21 | 广东志造生物科技有限公司 | A kind of D450 electronic yarn sizing agents and preparation method thereof |
| CN112973280A (en) * | 2021-02-05 | 2021-06-18 | 江苏九鼎新材料股份有限公司 | Method for manufacturing expanded glass fiber mesh cloth |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004003282A1 (en) | 2004-01-08 |
| CN100478516C (en) | 2009-04-15 |
| JP2004035280A (en) | 2004-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1304681C (en) | Collecting agent for glass fiber yarn and glass fiber yarn using the same | |
| JP6345404B2 (en) | Glass fiber sizing agent, glass fiber and glass fiber product coated with the same, and method for producing glass cloth. | |
| CN1191523A (en) | Forming size compositions, glass fibres coated with same and fabrics woven from such coated fibres | |
| US20050084675A1 (en) | Sizing composition for glass fibers | |
| CN1665978A (en) | Sizing agent for glass fiber yarn and glass fiber yarn using the sizing agent | |
| JP2008063713A (en) | Fiber treating agent and method for producing synthetic fiber using the same | |
| KR920009554B1 (en) | Glass fiber textile strands and improvements thereon | |
| CN100412019C (en) | Sizing agent for glass fiber yarn and glass fiber yarn using the sizing agent | |
| CN1131901C (en) | Beam for weaving and sizing method | |
| CN1333132C (en) | Collecting agent for glass fiber yarn and method for producing glass fiber yarn | |
| CN116535111B (en) | Impregnating compound for low-twist electronic grade glass fiber, preparation method and application thereof | |
| CN114436544B (en) | High-temperature starch type impregnating compound for electronic-grade glass fibers, and preparation method and application thereof | |
| TW201339117A (en) | Sizing agent for glass fiber and glass fiber fabric using the same | |
| JPWO2016063929A1 (en) | Textile glue | |
| CN1681857A (en) | Lubricated fluoropolymer yarn | |
| CN1109930A (en) | Oil composition used in fibre | |
| JP2004115350A (en) | Sizing agent for glass fiber yarn and glass fiber yarn using the same | |
| JP2004115351A (en) | Fiberglass yarn | |
| JP2017206787A (en) | Glass fiber strand, roving strand and manufacturing method of roving strand | |
| JP3837731B2 (en) | Glass fiber sizing agent and glass fiber to which the sizing agent is attached | |
| CN117486504B (en) | A high-temperature starch-type sizing agent for electronic-grade glass fiber yarn, and preparation method, product and application thereof | |
| JP2000191341A (en) | Sizing agent for glass fiber and glass fiber coated with this sizing agent | |
| JP2004027442A (en) | Method for producing glass fiber yarn | |
| JP2004026572A (en) | Sizing agent for glass fiber yarn and glass fiber yarn using the same | |
| JP2019112286A (en) | Glass fiber composite roving, method for producing glass fiber composite roving, and method for producing vehicular ceiling material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI HONGLIAN ELECTRON MATERIAL CO., LTD. Free format text: FORMER OWNER: ASAHI FIBER GLASS CO., LTD. Effective date: 20050826 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20050826 Address after: 201315 No. 121, South Road, Cambridge Industrial Zone, Shanghai, Pudong Applicant after: Shanghai Honglian Electronic Material Co.,Ltd. Address before: Tokyo, Japan Applicant before: ASAHI FIBER GLASS CO.,LTD. |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: Kangwu road 201315 Shanghai Pudong Kangqiao Industrial Zone No. 189 Patentee after: Shanghai Tianwei fiberglass Co.,Ltd. Address before: 201315 Shanghai, Cambridge Industrial Zone show along the road, No. 121, Pudong Patentee before: Shanghai Honglian Electronic Material Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170321 Address after: 200131 Chinese (Shanghai) free trade zone 215 Huashen Road No. 1 Building 1 room 1043 Patentee after: Shanghai Atlas Mstar Technology Ltd. Address before: Kangwu road 201315 Shanghai Pudong Kangqiao Industrial Zone No. 189 Patentee before: Shanghai Tianwei fiberglass Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090415 Termination date: 20170626 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |