JP2008266072A - Glass fiber manufacturing apparatus, glass fiber manufacturing method, and glass fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass fiber manufacturing apparatus which remarkably improves the manufacturing efficiency of glass fiber by removing bubbles during glass melting, to provide a glass fiber manufacturing method capable of obtaining the homogeneous glass fiber by using the apparatus, and to provide the glass fiber of a high grade obtained by the method. <P>SOLUTION: In the glass fiber manufacturing apparatus 10, a heat resistant nozzle 13 is provided on a base 12 of a heat resistant container 11, and spins the glass fiber F by continuously drawing out molten glass G from the heat resistant nozzle 1. A pressure resistant gas introducing tube 20 for introducing helium R or neon into an upper space of the molten glass G stagnating in the heat resistant nozzle 1 is installed. The method for manufacturing the glass fiber comprises introducing the helium or the neon into the heat resistant container 11, maintaining and adjusting the internal pressure of the container, continuously drawing out the molten glass G from the heat resistant nozzle 13 to spin the glass fiber F. The glass fiber F is manufactured by the glass fiber manufacturing method and has a fiber diameter of >3 μm and <9 μm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a glass fiber manufacturing apparatus used as a material constituting a printed wiring board and the like, a glass fiber manufacturing method using the manufacturing apparatus, and a glass fiber manufactured by the manufacturing method.

  Glass fiber, which has high performance as a structural material, has various requirements for the purpose of taking advantage of its excellent strength performance, from small devices created in the electronics industry to building materials used to construct huge buildings. One of the typical ways is a constituent material of a printed wiring board. Glass fiber used as a printed wiring board is generally manufactured by the following manufacturing method. First, various glass raw materials are weighed so as to have a predetermined glass composition, mixed raw material batches obtained by mixing are put into a glass melting furnace, heated to a temperature of 1500 ° C. or higher, and molten glass is obtained by vitrification reaction. To do. Next, the molten glass is subjected to various mixing operations to obtain a homogeneous state, and the molten glass that has become homogeneous flows into a molding apparatus connected to the glass melting furnace, that is, a bushing. Then, the glass fiber is rapidly cooled by continuously drawing out from a heat-resistant nozzle disposed on the bottom surface of the bushing controlled so as to be in a temperature state suitable for spinning the glass fiber. By using an applicator or the like, the glass fiber is wound up after a predetermined amount of a chemical such as a sizing agent is applied to the surface thereof to form a predetermined glass fiber wound body, and further subjected to various treatments. Applied to printed wiring boards.

  In order to manufacture a specific composite molded body using glass fiber as a constituent material of a printed wiring board, for example, the following steps are required. First, the glass yarn or glass yarn twisted yarn unwound from the package of the glass yarn wound body or glass yarn twisted yarn wound body is warped with a warper, and is secondarily sized by a gluing machine and wound from the beam to the room beam. This is the warp. The package of the glass yarn wound body is unwound, this is used for the weft, and the glass cloth is woven using an air jet loom or the like. Organic components adhering to the woven glass cloth are removed by heat incineration (heat deoiling), dipped in a treatment solution containing a silane coupling agent and dried (surface treatment), and then a matrix such as an epoxy resin A prepreg impregnated with resin is prepared. A laminate for a printed wiring board is manufactured by laminating one or a plurality of the prepared prepregs, attaching a conductor such as copper foil, and curing the resin by heating and pressing. The laminated plate is formed by forming a circuit pattern on conductors on both sides, forming a through hole with a drill or a laser, etc., and applying electroless copper plating, etc. A double-sided printed wiring board having a plated through hole as a conductor layer is manufactured. Furthermore, a multilayer printed wiring board is manufactured from a double-sided printed wiring board by a sequential molding method, a build-up molding method, or the like.

In recent years, with the dramatic development of the electronic component industry, various improvements have been made so that printed wiring boards are lighter and thinner and can be mounted at high density. In such efforts, various demands have been made for glass fibers, which are basic structural materials constituting printed wiring boards, and various improvements have been made to meet the demands. For example, Patent Document 1 discloses a treatment with a silane coupling agent and ammonium chloride as a method for preventing the generation of voids which are problematic when molding a printed wiring board. Patent Document 2 discloses an invention in which an epoxy resin is used as a primary sizing agent in order to improve warpage, twisting and the like that occur when a printed wiring board is thinned, and it can be dealt with by degreasing and opening treatment by water flow processing. Has been done. Further, Patent Document 3 discloses an invention in which a predetermined amount of a water-soluble urethane resin and / or a water-soluble epoxy resin is adhered to the glass surface in order to improve the change with time of the insulation resistance.
JP-A-6-112608 JP-A-9-67757 Japanese Patent Laid-Open No. 9-209233

  However, the inventions made so far are not sufficient from the viewpoint of realizing high-quality glass fibers used for printed wiring boards and the like for high-density mounting. Glass fiber is used in various applications, but in recent years by managing the fiber diameter of the glass fiber with higher accuracy than before, the strength of the composite material formed when the glass fiber is used as a composite material is high, In addition, it has been found that stable performance can be realized, and glass fibers having higher dimensional accuracy than conventional ones are required for many applications. In this way, glass fibers with a small fiber diameter are very important for achieving high performance by processing printed wiring boards with high accuracy when manufacturing printed wiring boards for high-density mounting. Yes. In addition, the demand for further downsizing and multi-functionalization of electronic devices has increased, and the wiring density of printed wiring boards incorporated in electronic devices has also increased. Due to the demand for high-density wiring, high-layering technology and micro-wiring technology have been introduced, and as a result, through holes or non-through holes (for making electrical connection between the conductor layers on both sides through the insulating layer) Hereinafter, when the through holes and the non-through holes are collectively referred to as “conduction holes”), the number of the through holes and the distance between the through holes are increased, and the insulation reliability between the conduction holes is more concerned than ever. It has become like this. On the other hand, for glass fibers used for printed wiring boards, hollow fibers called hollow fibers due to air bubbles mixed in the glass during the production of the glass fibers may occur very rarely. This hollow fiber not only greatly affects the physical performance such as the strength of the glass fiber, but also fatal defects such as poor insulation if the plating solution penetrates in the plating process of the conductive holes when producing printed wiring boards. Therefore, it is considered that this is a cause of a decrease in insulation reliability, and there is a concern that the increase in the number of holes in the printed wiring board and the narrowing of the spacing lead to a decrease in insulation reliability. Therefore, when manufacturing a printed wiring board, when glass fiber having a thin fiber diameter, ie, a fine count, is used, it is required that the glass fiber does not contain bubbles. In addition, as the glass fiber diameter becomes smaller, bubbles in the molten glass tend to cause fiber cutting during the production of the glass fiber. Also from the viewpoint of improvement, the presence of bubbles is not preferable.

  The present invention is a glass fiber manufacturing apparatus capable of dramatically improving the glass fiber manufacturing efficiency by completely removing bubbles mixed in the glass fiber at the time of glass melting and realizing a high yield rate. It is an object of the present invention to provide a glass fiber production method capable of obtaining homogeneous glass fibers using a glass fiber production apparatus, and to provide high-quality glass fibers produced by this production method.

  That is, the glass fiber production apparatus of the present invention is a glass fiber production apparatus that has a heat resistant nozzle on the bottom surface of the heat resistant container and continuously draws the molten glass from the heat resistant nozzle to spin the glass fiber. A pressure-resistant gas introduction pipe for introducing a gas containing 50% or more of helium and / or neon into the heat-resistant container is provided.

  Here, a glass fiber manufacturing apparatus having a heat-resistant nozzle on the bottom surface of the heat-resistant container and continuously drawing molten glass from the heat-resistant nozzle to spin glass fiber, the helium being contained in the heat-resistant container In addition, the fact that a pressure-resistant gas introduction pipe for introducing a gas containing 50% or more of neon is provided is as follows. That is, a plurality of nozzles made of a noble metal such as a platinum alloy having high heat resistance are arranged in the vertical direction, and the glass fiber material has a function of continuously drawing molten glass of glass fiber material from the nozzle tip hole. For glass fiber manufacturing equipment, molten glass is retained in a heat-resistant container provided with a nozzle, and used to introduce helium and / or neon having a concentration of 50% or more in volume% notation into the heat-resistant container. It represents that the gas inlet of the pressure-resistant gas inlet pipe is arranged in the heat resistant container.

  The present inventors have made various studies from the viewpoint of efficiently producing glass fibers, and provided a pressure-resistant gas introduction tube for introducing helium and / or neon into the heat-resistant container. Is introduced into a heat-resistant container, and the internal pressure of the upper space of the molten glass is maintained and adjusted to a pressure higher than atmospheric pressure, so that helium and neon are used for stable spinning of glass fibers having a high-precision fiber diameter. A role as a medium for pressurizing the molten glass and a role as an auxiliary for quickly releasing fine bubbles present in the molten glass from the molten glass to form a molten glass free of bubbles. I found a role to play.

  Regarding the first role, the internal pressure of the heat-resistant container is maintained and adjusted to a pressure higher than the atmospheric pressure, so that the molten glass in the heat-resistant container is stably drawn out from the nozzle on the bottom surface of the heat-resistant container. The fiber diameter does not vary from the glass fiber diameter, i.e., it cannot be made into a product, and a glass fiber having a stable precision can be obtained. As for the second role, helium and / or neon in contact with the molten glass staying in the heat-resistant container diffuses in the molten glass and reaches the bubbles in the molten glass, and then increases the size of the bubbles. As a result, the rising speed of the bubbles in the molten glass increases, and as a result, the bubbles are quickly removed from the molten glass. In order to sufficiently fulfill these two roles, it is necessary to introduce a gas containing 50% or more of helium and / or neon. If the concentration is less than 50%, both of these roles are sufficient. Can not be demonstrated. From the above viewpoints, when a higher level role is required for helium or neon, the concentration of helium and / or neon should be high, preferably 60% or more in volume% notation, More preferably, it is 70% or more in terms of volume%.

  As for gases other than helium and neon, various gases may be mixed as long as they do not adversely affect the homogeneity of the molten glass. For example, nitrogen, oxygen, hydrogen, carbon dioxide, carbon monoxide, Knox (NOx), sox (SOx), argon, and the like are applicable. For the concentration analysis of various gases to be mixed, a known measurement method and apparatus can be used as appropriate. For example, various devices such as a zirconia oxygen meter for oxygen, an infrared carbon dioxide concentration meter for carbon dioxide, and a noble gas such as helium and neon can be used such as a mass spectrometer and a heat conduction gas analyzer.

  About the heat-resistant container which comprises the glass fiber manufacturing apparatus of this invention, in addition to the heat resistant performance of 1000 degreeC or more, it exhibits the low reactivity with the molten glass of a high temperature state, and also the container inner wall of a heat resistant container with helium and neon Even if the container is kept in a pressurized state, it is necessary that the inner wall of the container in a high temperature state is not easily deformed, and it is sufficient if such a performance can be sufficiently realized with one structural member. However, when such high performance cannot be realized with only one structural member, a plurality of structural materials may be laminated, and a structure that selectively reinforces a mechanically weak part, By doing so, the desired mechanical performance may be obtained.

  For example, for a laminated structure, a ceramic refractory having heat resistance is constructed in a container shape, and a platinum rhodium alloy surface is formed by welding and lining a platinum rhodium alloy plate on the inner surface thereof. In order to suppress the deformation of the platinum rhodium alloy at a high temperature, a structure in which the outer periphery of the platinum rhodium alloy is covered with high-stiffness ceramics can be used to make use of the advantages of both materials. In addition, even when two or more types of structural members are used, the reinforcing structure is provided by reinforcing the outer periphery of the platinum rhodium alloy plate welded portion or the portion that is likely to be extended under heating conditions. It may be a thing.

  As for the dimensions of the heat-resistant container, an appropriately sized container can be adopted according to the amount of glass fiber spun, and the outer shape of the heat-resistant container is a shape having sufficient strength, which is more than necessary. There is no particular limitation as long as it does not require an outer shape.

  As for the pressure-resistant gas introduction pipe, if it is made of a material capable of introducing helium or neon into the heat-resistant container in addition to the predetermined heat resistance, its shape such as its inner diameter and outer diameter, and its dimensions such as length Is not limited. In addition, pressure-resistant gas introduction pipes include manometers, flow meters, temperature control devices such as heating and cooling devices to adjust the gas temperature, thermometers, dehumidification devices, hygrometers, mass analyzers, and pressure controls. An appropriate number of filter equipment such as a device or a dust removal filter may be arranged at an appropriate position, and the number of pressure gas introducing pipes may be one or two or more.

  The location where the pressure-resistant gas introduction tube is disposed in the heat-resistant container is not particularly limited except for a portion that affects the glass fiber to be spun, such as in the vicinity of the heat-resistant nozzle from which the molten glass is continuously drawn. Further, it is not necessary that the pressure-resistant gas introduction pipe is disposed in the heat-resistant container, and there may be a plurality of places. The part that affects the glass fiber is, for example, a part that varies the fiber diameter of the glass fiber, that is, affects the flow rate, temperature, etc. of the molten glass.

  In addition, regarding the shape and dimensions of the heat-resistant nozzle, and the method of disposing it in the heat-resistant container, glass fibers of a predetermined size and shape can be continuously spun and molded, and glass fibers can be produced over a long period of time. As long as an overload stress is not applied to the arrangement location, any configuration may be used.

  Furthermore, the arrangement of the heat-resistant nozzles in the heat-resistant container is an arrangement that allows efficient spinning, and by arranging a plurality of heat-resistant nozzles on the bottom surface of the heat-resistant container at appropriate intervals, What is necessary is just to be able to smoothly draw out the molten glass from the heat resistant nozzle.

  In addition to the above, the glass fiber manufacturing apparatus of the present invention further includes a container internal pressure adjusting means for maintaining and adjusting the internal pressure of the upper space of the molten glass into which helium and / or neon is introduced in the heat-resistant container. If it has, since the molten glass is continuously drawn out from the nozzle while the internal pressure of the glass fiber production apparatus is maintained within a predetermined stable range, the fiber diameter is free from dimensional deviation from the target glass fiber diameter. The glass fiber which has can be manufactured.

  Here, what has a container internal pressure adjusting means for maintaining and adjusting the internal pressure of the upper space of the molten glass introduced with helium and / or neon in the heat resistant container to a pressure higher than the atmospheric pressure is in the heat resistant container. Whether the upper and lower limits of the pressure value in the heat-resistant container due to helium and neon filling are set in advance, and helium and neon are released outside the device so that the pressure value does not exceed the upper and lower limits An internal pressure regulator that has a function of maintaining a pressure internal pressure higher than the atmospheric pressure by efficiently accumulating or controlling the flow rate of helium or neon to decrease or increase, or both, is glass. It shows that it is connected to the fiber manufacturing apparatus.

  The internal pressure of the device is a value measured by a measuring device such as a manometer disposed in the heat-resistant container, and this measured value can also be accumulated for adjusting the pressure in the control system. Even if the control system of the internal pressure regulator is an on / off control system that uses an open / close valve, etc., the opening cross-sectional area of the inlet port from the pressure-resistant gas introduction pipe introducing helium or neon to the heat-resistant container is continuously controlled. It is possible to use either a method of adjusting by adjusting, a method of adjusting by continuously controlling the opening cross-sectional area of the outlet for exhausting helium or neon, or a combination of these. .

  The upper and lower pressure values should be set according to the inner diameter of the nozzle and the viscosity of the molten glass, and should be changed to appropriate values according to other settings such as spinning temperature and glass fiber diameter. Can do.

  In addition to the above, the glass fiber manufacturing apparatus of the present invention has the following means for supplying the molten glass body into the heat-resistant container. That is, the glass fiber manufacturing apparatus of the present invention has a structure in which a charging device for continuously or intermittently supplying glass suitable for the amount of molten glass drawn from the nozzle into the heat resistant container is disposed in the heat resistant container. With such a structure, it is possible to keep an appropriate amount of molten glass in the heat-resistant container according to the drawing conditions of the glass fiber, and a predetermined stable glass. This is preferable because the fiber production conditions can be maintained.

  Moreover, about the glass composition of the glass supplied, various glass compositions currently used as a glass material for glass fiber use are applicable. For example, various glass fibers such as E glass, D glass, AR glass, T glass, S glass, H glass, and C glass can be used, and even newly developed glass materials can be melted from the nozzle. Any glass material can be adopted as long as the material is designed in accordance with the manufacturing method for drawing out and forming the glass.

  As for the glass supplied into the heat-resistant container, whether it is solid glass, molten glass, or any size or shape, the glass fiber production apparatus of the present invention can be used. Anything that is suitable for input can be used. That is, for example, the crushed glass cullet may be formed into a fixed shape such as glass marble or glass rod, or may be high-temperature molten glass. The supplied glass may be mixed with crystals or may contain a large number of bubbles. Moreover, the supplied glass can be obtained by adopting a known melting method or manufacturing method.

  In addition to the above, the glass fiber production apparatus of the present invention is preferably a marbled glass body to be fed into the heat-resistant container because the charging operation by the charging means for supplying at a predetermined speed becomes easy.

  Marble glass is a solid glass that has a substantially spherical outer shape, and has an outer shape that can be regarded as a substantially spherical shape, in which a shear mark generated when a predetermined amount of the molten glass is cut may be present on the surface thereof. .

  About the manufacturing method of marble glass, what kind of manufacturing method may be adopted and bubbles may be contained as described above, but the crystal is not contained as much as possible. It is preferable. Further, the size of the marble glass may be adopted as long as it has a size commensurate with the means for charging into the heat resistant container.

  In addition to the above, the glass fiber manufacturing apparatus of the present invention is an auxiliary device such as a gauge for measuring the amount of molten glass in a heat-resistant container, a temperature measuring device for molten glass, an exhaust gas treatment device, and an energizing device for indirect heating. As many devices as needed can be placed in place.

  The glass fiber manufacturing method of the present invention is a glass fiber manufacturing method in which molten glass is continuously drawn out from a heat-resistant nozzle provided on the bottom surface of the heat-resistant container in addition to the above, and then spun into the glass. Helium and / or neon is introduced to maintain and adjust the internal pressure of the upper space of the molten glass in the container at a pressure higher than atmospheric pressure.

Here, it is a method for producing a glass fiber in which molten glass is continuously drawn out from a heat resistant nozzle provided on the bottom surface of the heat resistant container and spun, and helium and / or neon is introduced into the heat resistant container. Maintaining and adjusting the internal pressure of the upper space of the molten glass in the container to a pressure higher than atmospheric pressure is as follows. That is, using a glass fiber manufacturing apparatus that has a heat-resistant nozzle on the bottom surface of the heat-resistant container and continuously draws the molten glass from the heat-resistant nozzle and spins the glass fiber. Since a pressure-resistant gas introduction pipe for introducing neon is provided, helium and / or neon introduced from the pressure-resistant gas introduction pipe stagnates in the upper space of the molten glass in the container. By maintaining and adjusting the internal pressure of the upper space so as to be a predetermined high pressure, the molten glass staying in the heat resistant container is rapidly cooled to a glass fiber by stably extracting a predetermined amount from the heat resistant nozzle. Represents. In order to pull out a glass fiber having a stable fiber diameter from the nozzle, it is preferable to maintain and adjust the internal pressure of the upper space of the molten glass at a pressure of 500 mmH ₂ O or higher, that is, 4903.5 Pa (Pascal) or higher than the atmospheric pressure. Furthermore, in order to cope with a thin fiber diameter and high-speed production conditions with a margin, it is better to maintain and adjust at a pressure of 700 mmH ₂ O or more, that is, 6864.9 Pa or more than atmospheric pressure, and more preferably from atmospheric pressure. Is maintained and adjusted at a pressure of 900 mmH ₂ O or more, that is, 8826.3 Pa or more.

  In order to maintain and adjust the internal pressure of the upper space of the molten glass in the heat-resistant container to a desired pressure higher than atmospheric pressure, not only the pressure-resistant gas introduction pipe but also a meter and an exhaust port for measuring the internal pressure in the heat-resistant container By arranging it, it is necessary to manage the gas pressure of helium or neon, and a stable internal pressure can be realized by operating so as to adjust the pressure in conjunction with the measurement result.

  In addition, the internal pressure of the upper space of the molten glass in the heat-resistant container is the problem of production hindrance such as yarn breakage or the pressure resistance of the heat-resistant container in order to obtain glass fibers having a desired fiber diameter or to obtain a desired draw amount. It can be changed as long as it does not cause problems such as performance, and is not particularly limited.

  Moreover, if the manufacturing method of the glass fiber of this invention heats and holds the molten glass in a heat resistant container at 1200 degreeC or more in addition to the above, generation | occurrence | production of the defect in molten glass, such as devitrification, will be suppressed reliably. However, it is possible to smoothly manufacture glass fibers having a desired fiber diameter by maintaining the proper viscosity of the molten glass.

  Here, holding the molten glass in the heat-resistant container at 1200 ° C. or higher was measured with a measurement accuracy of about ± 5 ° C. by using various temperature measuring devices such as a thermocouple thermometer and an optical pyrometer. This means that the heating source is adjusted based on the temperature of the molten glass, and the molten glass temperature is maintained at 1200 ° C. or higher. As for the type of the heat source, heating by electricity is preferable, but other than that, radiation heating or heating by combustion of gas, solid, or liquid fuel may be adopted.

  If the molten glass in the heat-resistant container is less than 1200 ° C., the glass may easily precipitate crystals in the heat-resistant container, and as a result, the glass fiber is cut by foreign matter crystallized during spinning, or glass Devitrification deteriorates properties such as strength of the glass fiber, which is not preferable.

  In addition to the above, the method for producing the glass fiber of the present invention is a material having a high chemical durability as long as the molten glass is any one of alkali-free glass, aluminosilicate glass, borosilicate glass, and zirconia silicate glass. Therefore, it is particularly suitable for glass fibers used in applications exposed to various chemicals and applications requiring attention to environmental performance.

Here, the molten glass is any one of alkali-free glass, aluminosilicate glass, borosilicate glass, and zirconia silicate glass. The material of the molten glass substantially contains alkali metal element components, that is, sodium, potassium, and lithium. It is a glass composition that does not contain, or is a material in which aluminum and silicon are main components, that is, the total amount of Al ₂ O ₃ and SiO ₂ exceeds 60% when the glass composition is expressed in terms of mass percentage in terms of oxides. Or, when boron and silicon are the main components, that is, when the glass composition is expressed in terms of mass percentage in terms of oxide, the total content of B ₂ O ₃ and SiO ₂ exceeds 70%, or zirconia and silicon the major components, i.e. if the ZrO ₂ and SiO ₂ to represent the glass composition as represented by mass percentage terms of oxides It means that but is any material that more than 60%. In addition, “substantially not contained” means that the inclusion of an alkali metal component as an impurity component unintentionally mixed from a glass raw material, refractory, etc. is recognized. Specifically, an alkali metal element component is oxidized. Any material that is less than 1% in terms of mass percentage in terms of physical properties may be used.

  The glass fiber production method of the present invention is most preferably the so-called indirect molding method MM method (the marble melt method). However, a bushing is used to produce a large amount of glass fiber as necessary. The DM method (direct melt method) may be applied using an apparatus. In order to apply the glass fiber manufacturing method of the present invention to the DM method, for example, a high-precision fiber can be obtained by a method similar to the case of the MM method by forming a molding region after the feeder portion of the glass melting furnace in a sealed structure. A glass fiber having a diameter and no bubbles can be produced.

  The glass fiber of the present invention is produced by the glass fiber production method described above, and has a fiber diameter of more than 3 μm and less than 9 μm.

  Here, it is manufactured by said manufacturing method of glass fiber, and that the fiber diameter exceeds 3 micrometers and is less than 9 micrometers is as follows. That is, a glass fiber manufacturing method in which molten glass is drawn from a heat resistant nozzle provided on the bottom surface of a heat resistant container and spun, and helium and / or neon is introduced into the heat resistant container so that the internal pressure of the container is higher than atmospheric pressure. The average fiber diameter of the glass fiber obtained by the glass fiber production method in which the molten glass is continuously drawn out from the heat-resistant nozzle by spinning and maintaining the high pressure by maintaining the high pressure is thicker than 3 μm and thinner than 9 μm. It is a thing.

  Even if the glass fiber diameter is less than 3 μm, it is possible to manufacture if the effort for manufacturing, management and maintenance of the high-precision nozzle required for manufacturing is not required, but it is the most efficient manufacturing Is possible when the average fiber diameter exceeds 3 μm. A fiber diameter exceeding 9 μm is not preferable because the fiber diameter is unsuitable for printed wiring boards that require high-density mounting, for example. From the above viewpoint, if it is limited to being applied to a high-density printed wiring board, the glass fiber diameter is preferably larger than 3 μm and smaller than 7 μm, more preferably larger than 3 μm and smaller than 6 μm. That is.

  In addition to the above, the glass fiber of the present invention is glass fiber as long as the helium and / or neon content in the glass fiber is in the range of 0.01 to 2.0 μL / g (0 ° C., 1 atm). Since the fine bubbles inside are removed, a high degree of homogeneity can be realized.

  When the total content of helium and / or neon in the glass fiber is in the range of 0.01 to 2.0 μL / g (0 ° C., 1 atm), the glass is analyzed by performing a gas analysis with a quadrupole mass spectrometer. It means that the total amount of helium and neon in the fiber is in the range of 0.01 μL / g (0 ° C., 1 atm) to 2.0 μL / g (0 ° C., 1 atm). .

  If the total content of helium and / or neon in the glass fiber is less than 0.01 μL / g (0 ° C., 1 atm), the function of removing bubbles from the glass fiber cannot be sufficiently performed. On the other hand, even if a large amount of gas is introduced until the total content of helium and / or neon in the glass fiber exceeds 2.0 μL / g (0 ° C., 1 atm), the effect of removing bubbles is further promoted. That is not to say, the effort to introduce a large amount of gas is wasted. From the above viewpoint, the total content of helium and / or neon in the glass fiber is 0.01 to 2.0 μL / g (0 ° C., 1 atm), more preferably 0.01 to 1.0 μL / g (0 ° C., 1 atm).

  Further, the glass fiber of the present invention can be used for various applications as long as the product form after being molded is any of chopped strands, yarns, and rovings.

  Here, the chopped strand is a short fiber having a predetermined length, the yarn is a continuous filament that is twisted, and the roving is a strand in which a plurality of strands are arranged.

  About a chopped strand, the length dimension and fiber diameter are not limited. About the length dimension and fiber diameter of a fiber, what was adapted for a use can be selected. Further, any method for producing chopped strands can be adopted. The glass fiber drawn and drawn from the nozzle can be cut directly by a cutting device, or the drawn glass fiber can be wound once and cut by a cutting device depending on the application. In this case, any method can be adopted as a cutting method. For example, an outer peripheral blade cutting device, an inner peripheral blade cutting device, a hammer mill, or the like can be used.

  As for the yarn, as long as a predetermined twist is imparted, the size and direction of the twist including the non-twisted yarn are not particularly limited.

  In addition, for roving, a plurality of strands are arranged and bundled, and if they are wound in a cylindrical shape, the wound fiber diameter and the aligned alignment can be used without any problem. The number is not limited.

  In addition to the above, the glass fiber of the present invention can be used in the form of a continuous strand mat, a bonded mat, a cloth, a tape, a braided fabric, a milled fiber, or the like. Moreover, it can also be set as the prepreg and LFTP pellet which impregnated resin. And for usage and molding methods that apply glass fiber, spray-up, hand lay-up, filament winding, injection molding, centrifugal molding, press molding, roller molding, BMC using match die, SMC method, etc. Can respond.

  The glass fiber of the present invention can be given various performances by applying various surface treatment agents. For example, sizing agent, binding agent, coupling agent, lubricant, antistatic agent, emulsifier, emulsion stabilizer, pH adjuster, antifoaming agent, colorant, antioxidant, hindering agent or stabilizer, etc. Alternatively, an appropriate amount of a plurality of types can be combined and applied to the surface of the glass fiber to coat it. Further, such a surface treatment agent or coating agent may be a starch type or a plastic type.

  For example, in the case of a sizing agent for FRP, acrylic, epoxy, urethane, polyester, vinyl acetate, vinyl acetate / ethylene copolymer, and the like can be used as appropriate.

  If the glass fiber of the present invention is a glass yarn used for a printed wiring board in addition to the above, it has a uniform and high quality even when drilling or laser processing is required for use on the printed wiring board. Since it is made of glass fiber, it is easy to apply high-precision processing to the substrate.

  The glass yarn used for the printed circuit board is made of glass filaments having an average fiber diameter larger than 3 μm and a fiber diameter of up to 9 μm, and is focused by attaching a sizing agent to 10 to 500 glass filaments. The strand is twisted.

  As described above, the glass fiber of the present invention can be used alone or in combination as a sizing agent used for sizing the glass filaments constituting the yarn. Of these, starch is most often used. Starch focuses glass filaments and is used as a film-forming agent for the surface of glass fiber to protect the surface of glass yarn from bending and friction during the process. It is used.

  Moreover, although the glass fiber of this invention has the most preferable use for printed wiring boards, you may use it for various uses as needed. Specifically, it can be used for the following purposes. For example, for applications related to electronic equipment, insulating plates, terminal boards, IC substrates, display substrates, electronic equipment housing materials, gear tape reels, various storage cases, optical component packages, electronic component packages, switch boxes, Insulation supports, etc. For automotive applications, body roof materials (roof materials), window frame materials, glazing, vehicle body front, car bodies, lamp houses, air spoilers, fender grills, tank trolleys, ventilators, water tanks , Waste tank, seat, nose cone, fender grill, curtain, filter, air conditioner duct, muffler filter, dash panel, fan blade, radiator tire, timing belt, etc. For aircraft related applications, engine cover, air duct, seat frame ,container, There are martens, interior materials, service trays, tires, anti-vibration materials, timing belts, etc. For shipbuilding and land transportation, motor boats, yachts, fishing boats, domes, buoys, marine containers, floaters, tanks, traffic lights, road signs , Curve mirrors, containers, pallets, guardrails, lighting covers, spark protection sheets, etc., and agriculture related applications include greenhouses, silo tanks, spray nozzles, struts, linings, soil conditioners, construction, civil engineering, For building materials, bathtubs, bath / toilet units, toilets, septic tanks, water tanks, interior panels, capsules, valves, knobs, wall reinforcements, precast concrete boards, flat plates, parallel boards, tents, shutters, exterior panels, sashes, Plumbing pipe, reservoir, pool, road, structure side wall, concrete There are frames, tarpaulins, waterproof linings, curing sheets, insect nets, etc. For industrial facilities, bug filters, sewer pipes, water purification equipment, anti-vibration concrete reinforcement (GRC), water tanks, belts, chemical tanks , Reaction vessels, containers, fans, ducts, corrosion-resistant linings, valves, refrigerators, trays, freezers, troughs, equipment parts, motor covers, insulated wires, transformer insulation, cable cords, work clothes, curtains, evaporation panels, equipment housings, etc. There are fishing rods, skis, archery, golf clubs, pools, canoes, surfboards, camera housings, barrels, helmets, shock protection armor, flower pots, display boards, etc. Then there are tables, chairs, beds, benches, mannequins, trash cans, mobile device protection materials, etc. is there. Further, the glass fiber of the present invention can be used alone. For example, in a liquid crystal display device used as a display device for a liquid crystal television or a personal computer, the fiber diameter of the glass fiber has a stable dimensional accuracy as a liquid crystal spacer used for maintaining a distance between two substrate glasses. Therefore, it is preferable.

  (1) As described above, the glass fiber manufacturing apparatus of the present invention has a heat resistant nozzle on the bottom surface of the heat resistant container, and continuously draws the molten glass from the heat resistant nozzle to spin the glass fiber. In the glass fiber manufacturing apparatus, a pressure-resistant gas introduction pipe for introducing a gas containing 50% or more of helium and / or neon into the upper space of the molten glass staying in the container is provided in the heat resistant container. As a result, helium and / or neon diffuses into the molten glass, and fine bubbles present in the molten glass are quickly and completely removed to produce glass fibers free of bubbles with a high yield. Make it possible.

  (2) The glass fiber manufacturing apparatus according to the present invention also includes a container internal pressure adjustment for maintaining and adjusting the internal pressure of the upper space of the molten glass into which helium and / or neon is introduced in the heat resistant container at a pressure higher than the atmospheric pressure. If there is a means, it is easy to maintain stable production conditions in the production of continuous glass fiber, and for this reason, fluctuations in glass fiber production quality such as fluctuations in glass fiber diameter are suppressed. Thus, it is possible to manufacture glass fiber products of uniform quality.

  (3) Furthermore, if the glass fiber manufacturing apparatus of the present invention has a charging means for supplying the molten glass body into the heat-resistant container, a glass object whose properties and foam quality are known in advance is used. By properly setting the production conditions according to the foam quality and the like, it becomes possible to spin glass fibers of stable quality.

  (4) Moreover, the glass fiber manufacturing apparatus of the present invention can reliably remove bubbles even when bubbles are present in the marble glass if the glass melt is marble glass. It is possible to produce glass fibers that do not contain bubbles.

  (5) The glass fiber manufacturing method of the present invention is a glass fiber manufacturing method in which molten glass is continuously drawn out from a heat-resistant nozzle provided on the bottom surface of a heat-resistant container and then spun. Since helium and / or neon is introduced and the internal pressure of the upper space of the molten glass in the container is maintained and adjusted to a pressure higher than atmospheric pressure, the pressure by helium and / or neon is adjusted according to the glass fiber diameter. It is easy to keep the fluctuation of the fiber diameter within a small range, and a glass fiber with high dimensional accuracy can be manufactured with high efficiency.

  (6) The glass fiber manufacturing method of the present invention realizes sufficient temperature conditions for spinning glass fibers into fibers as long as the molten glass in the heat-resistant container is heated to 1200 ° C. or higher. Further, it can be produced under preferable conditions from the viewpoint of suppressing the crystallization of crystals in the molten glass and promoting the defoaming of bubbles.

  (7) Further, the glass fiber production method of the present invention is required to have high chemical durability if the molten glass is any of alkali-free glass, aluminosilicate glass, borosilicate glass, and zirconia silicate glass. It is suitable for producing glass fibers capable of exhibiting excellent performance according to applications such as applications requiring high electrical insulation resistance and applications requiring high dimensional stability.

  (8) The glass fiber of the present invention is produced by the glass fiber production method of the present invention, and has a fiber diameter of more than 3 μm and less than 9 μm. We can supply customers with a lot of glass fiber with no stable fiber diameter.

  (9) In addition to high performance, the glass fiber of the present invention has a helium and / or neon content in the glass fiber in the range of 0.01 to 2.0 μL / g (0 ° C., 1 atm). Defect-free glass fiber with excellent appearance quality.

  (10) If the glass fiber of the present invention is a glass yarn used for a printed wiring board, it can be applied to a printed wiring board used for thinning and weight reduction, and also for high-density mounting. It has excellent properties with easy quality.

  EXAMPLES The glass fiber manufacturing apparatus of the present invention, the glass fiber manufacturing method performed using the glass fiber manufacturing apparatus of the present invention, and the glass fiber obtained by this manufacturing method will be described based on examples. .

  FIG. 1 is a cross-sectional explanatory view of the glass fiber manufacturing apparatus of the present invention. In this figure, 10 is a glass fiber manufacturing apparatus, 11 is a heat-resistant container, 12 is a bottom surface of the heat-resistant container, 13 is a heat-resistant nozzle disposed on the bottom surface, and 20 is a pressure-resistant gas introduction tube for introducing helium or neon. , 30 is a raw material glass charging device, 31 is an adjustment door of the raw material glass charging device, 32 is a charging door of the raw material glass charging device, 40 is an exhaust gas discharge pipe, 50 is a heating element, G is molten glass, F is glass fiber, M Represents marble glass, and R represents helium gas.

This glass fiber manufacturing apparatus 10 is an equipment for manufacturing fine count products of E glass yarn used for printed wiring boards, but glass fiber products used for printed wiring boards require high homogeneity. intended to be, 1 × 10 but ⁶ becomes required no more than one bubble quality and in m, in the conventional manufacturing equipment difficult to continue to keep the foam quality at a high level, a problem that therefore production efficiency is reduced was there. For this reason, the glass fiber manufacturing apparatus 10 shown in FIG.

  This glass fiber manufacturing apparatus 10 has 400 nozzles 13 made of platinum rhodium alloy for fine counts arranged at equal intervals on the bottom surface 12 of a heat-resistant container 11 made of platinum rhodium alloy by welding, and the temperature condition is set. By adjusting the temperature of the molten glass G in the vicinity of the bottom surface 12 of the heat resistant container 11 by adjusting with the electric heating element 50 arranged around the heat resistant container 11, the fiber from the heat resistant nozzle 13 Glass fiber F having a diameter of 4.1 μm can be drawn continuously. Moreover, it can manufacture also about the glass fiber F with a fiber diameter of 6.4 micrometers by changing various temperature conditions.

  Next, a method for producing glass fiber F by the glass fiber production apparatus 10 will be specifically described.

  A blending raw material batch obtained by preparing various glass raw materials so as to have an E glass composition which is also alkali-free glass and aluminosilicate glass in advance is melted in a platinum alloy melting furnace, and then the molten glass is a marble molding machine. Then, a marble glass M having an average diameter of 20 mm is molded and prepared using a marble molding machine. This marble glass M contains 10 bubbles / 100 g or more of bubbles, and is a glass obtained by processing a molten glass cut from a gob into a marble shape. Therefore, a thin shear mark remains on the surface.

  Next, the marble glass M is introduced into the apparatus 30 from the adjustment door 31 of the raw glass feeding apparatus 30 disposed in the upper part of the heat-resistant container 11 of the glass fiber production apparatus 10. Thereafter, the adjustment door 31 is closed and sealed, and then the marble door M is thrown into the heat-resistant container 11 of the glass fiber manufacturing apparatus 10 with the closing door 32 being opened. This series of operations of the raw glass feeding apparatus 30 is performed by automatic control by setting a program in advance, but if necessary, manual operation is also possible.

Since the glass marble M put into the heat-resistant container 11 is heated so that the liquid surface temperature of the molten glass G becomes 1440 ° C. or higher, it immediately softens and becomes a molten state. A gas introduction port of a pressure-resistant gas introduction pipe 20 for introducing helium gas R is disposed on the upper portion of the heat-resistant container 11 corresponding to the upper surface of the molten E glass. The pressure-resistant gas introduction pipe 20 is provided with a manometer (not shown) and measures the pressure of the helium gas R introduced into the heat-resistant container as needed. The pressure condition of the helium R in the heat-resistant container 11 is provided by arranging a device for automatically fine-tuning the valve of the helium cylinder using the introduction pressure of the helium R from the helium gas cylinder as a container internal pressure adjusting means according to the measurement result. Is always adjusted to be 900 mmH ₂ O higher than atmospheric pressure.

  Further, an exhaust gas discharge pipe 40 for discharging exhaust gas such as gas generated from the molten glass to the outside of the system is provided at the upper part of the heat resistant container 11. By the action of the exhaust gas discharge pipe, the helium pressure and the helium concentration in the heat resistant container 11 are maintained in a constant state. The helium concentration here is 85% in volume concentration display when the concentration is measured.

  The helium gas R introduced from the pressure-resistant gas introduction pipe 20 has two main functions in this glass fiber manufacturing method. The first important function is that the internal pressure in the heat-resistant container 11 is maintained and adjusted to a pressure higher than atmospheric pressure, and an appropriate pressure is selected and maintained within a predetermined range. As a result, the flow rate of the molten glass G from the nozzle 13 becomes appropriate, and as a result, a glass fiber having a stable fiber diameter is obtained. The second important function of the helium gas R is to act as an auxiliary agent for degassing fine bubbles in the molten glass.

  The first function, that is, the function of maintaining and adjusting the internal pressure in the heat-resistant container 11 to a pressure higher than the atmospheric pressure, the molten glass G is continuously drawn out from the heat-resistant nozzle 13 and rapidly cooled to become glass fibers. A bundling agent (also referred to as a sizing agent) prepared on the surface is applied by an applicator (not shown), and 400 glass filaments are bundled to form a glass strand, which is wound around a tube attached to a winder having a winder. It is made into a glass fiber wound body called a cake.

In order to realize the second function, that is, the function of facilitating degassing of bubbles, the helium gas R needs to diffuse through the molten glass and reach the fine bubbles in the molten glass. In the glass fiber produced by using, a behavior that the content of helium increases as a trace of the production is recognized. About the glass fiber which consists of E glass manufactured by various setting conditions mentioned above, the content of helium in the manufactured glass fiber was measured. For this measurement, a quadrupole mass spectrometer (QME125) manufactured by BALZERS, which is equipped with a secondary electron multiplier (SEM) and has improved measurement sensitivity, was used. In the gas analysis by the quadrupole mass spectrometer, a glass sample to be measured is put in a platinum dish, and the platinum dish is held in a sample chamber to be in a vacuum state of 10 ⁻⁵ Pa (that is, 10 ⁻⁸ Torr). The gas released by heating was introduced into a quadrupole mass spectrometer having a measurement sensitivity of 0.001 μL / g for analysis. In order to investigate the number of bubbles in the glass fiber of the present invention, the number of bubbles is measured with a stereomicroscope of 20 to 100 times while holding the glass fiber in an immersion liquid having the same refractive index as that of the glass fiber. went.

As a result, the glass fiber of the present invention has an average fiber diameter of 4.1 μm, the helium content in the glass is 0.51 μL / g (0 ° C., 1 atm), and the bubbles in the glass fiber are It was found that the quality was 1 or less at 1 × 10 ⁷ m.

  Further, the glass fiber cake manufactured by the above-described manufacturing method further unwinds the strand from this cake, performs twisting while applying a twist of 0.3 times / inch in the Z direction, It was prepared and wound around a glass yarn bobbin to form a glass yarn wound body. Subsequently, the glass yarn released from the glass yarn wound body was used to warp with a warper to obtain warp, and the glass yarn was used as a weft to plain weave with a high-speed air jet loom to weave a glass cloth. When this glass cloth was used to mold a prepreg, a printed wiring board was manufactured and evaluated whether there was any problem in its performance, it was found that there was no problem at all and high performance could be realized as a printed wiring board.

  As described above, by using the glass fiber manufacturing apparatus of the present invention, the glass fiber of the present invention manufactured by the glass fiber manufacturing method of the present invention has high homogeneity even if it is a fine glass fiber. It was clarified that it has excellent quality with the inclusion of air bubbles suppressed. Moreover, it became clear that the manufacturing method of the glass fiber of this invention can implement | achieve a high yield rate, and can suppress generation | occurrence | production of the cutting defect of glass fiber. Furthermore, it has also been clarified that the glass fiber manufacturing apparatus of the present invention has performance indispensable for efficiently manufacturing glass fibers with high homogeneity such as a printed wiring board.

Cross-sectional explanatory drawing of the glass fiber manufacturing apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Glass fiber manufacturing apparatus 11 Heat resistant container 12 Bottom surface 13 Heat resistant nozzle 20 Pressure-resistant gas introduction pipe 30 Raw material glass charging device 31 Adjustment door of raw material glass charging device 32 Input door of raw material glass charging device 40 Exhaust gas discharge pipe 50 Heating element G Melting Glass F Glass fiber M Marble glass R Helium gas

Claims (10)

A glass fiber manufacturing apparatus that has a heat resistant nozzle on the bottom surface of the heat resistant container and spins the glass fiber by continuously drawing the molten glass from the heat resistant nozzle,
A glass having a pressure resistant gas introduction pipe for introducing a gas containing helium and / or neon in an amount of 50% or more into the upper space of the molten glass staying in the heat resistant container. Textile manufacturing equipment.   The container internal pressure adjusting means for maintaining and adjusting the internal pressure of the upper space of the molten glass into which helium and / or neon is introduced in the heat-resistant container is higher than the atmospheric pressure. Glass fiber manufacturing equipment.   The glass fiber manufacturing apparatus according to claim 1 or 2, further comprising a charging means for supplying the glass melt body into a heat-resistant container.   The glass fiber manufacturing apparatus according to claim 3, wherein the glass melt is a marble glass. A glass fiber manufacturing method for continuously drawing and spinning molten glass from a heat-resistant nozzle provided on the bottom surface of a heat-resistant container,
A method for producing glass fiber, wherein helium and / or neon is introduced into the heat-resistant container to maintain and adjust the internal pressure of the upper space of the molten glass in the container at a pressure higher than atmospheric pressure.   The method for producing glass fibers according to claim 5, wherein the molten glass in the heat-resistant container is heated and held at 1200 ° C or higher.   The method for producing glass fibers according to claim 5 or 6, wherein the molten glass is any one of alkali-free glass, aluminosilicate glass, borosilicate glass, and zirconia silicate glass.   A glass fiber produced by the method for producing glass fiber according to any one of claims 5 to 7, wherein the fiber diameter is more than 3 µm and less than 9 µm.   The glass fiber according to claim 8, wherein the glass fiber has a helium and / or neon content in a range of 0.01 to 2.0 μL / g (0 ° C., 1 atm).   The glass fiber according to claim 8 or 9, wherein the glass fiber is a glass yarn used for a printed wiring board.

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