JP2012001434A - Bushing for producing long glass fiber and method for producing the same, and apparatus for producing long glass fiber and method for producing long glass fiber using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable to diminish evaporant from a bushing, strengthen the structure of the bushing, and form glass fiber having high accuracy.SOLUTION: In a bushing 1 for an apparatus for producing long glass fiber, molten glass G is let out from nozzles 6 attached to a bushing plate 4 to form glass filaments F. Film is not formed in a region adjacent to the nozzles not less than 1 mm away from a position corresponding to a boundary of the nozzles 6 on the outer surface of the bushing plate 4. A film 7 is formed in a region other than the region adjacent to the nozzles on the outer surface. The film 7 is formed using any one of the material group consisting of ceramics, glass ceramics, and glass.

Description

  The present invention relates to a bushing used when molding a long glass fiber, a method for manufacturing the bushing, a glass long fiber manufacturing apparatus having the bushing as a main component, and manufacturing a glass long fiber using the apparatus. In particular, the present invention relates to an improvement in outer surface properties of a bushing for producing glass long fibers.

  In general, glass fibers are broadly classified into short glass fibers and long glass fibers. Of these, long glass fibers that are surely excluded from short glass fibers are molded or spun. A container with a molding nozzle having heat resistance called a bushing is used. This bushing is used to form molten glass into a fiber shape. A bushing plate is fixed to the bottom of the bushing peripheral wall to form a bushing body (container body), and the interior of the bushing body is melted. In addition to the glass supply space, a large number of nozzles for allowing the molten glass from the molten glass supply space to flow out are provided on the bottom side of the bushing plate. And after making molten glass flow out continuously from this many nozzles, many glass filaments (glass long fiber) are formed, respectively, and after applying coating agents, such as a sizing agent, on the surface of this glass filament A fiber product made of long glass fiber is manufactured by winding it with a winder as a strand.

  In order to produce various types of long glass fibers of high quality continuously and smoothly by the above process, a bushing suitable for the performance, shape, dimensions, etc. required for the produced glass fibers is required. For this reason, until now, many inventions have been made on bushings and nozzles arranged on them. For example, Patent Document 1 and Patent Document 2 disclose spinning nozzle tips for producing long glass fibers having a deformed cross-sectional shape with an aspect ratio of 2 or more or 4 or more. In addition, the bushing plate is softened and deteriorated when held for a long time in a high temperature state and causes a drooping deformation due to its own weight or the weight of the molten glass. Patent Document 3 describes a holding for preventing this deformation. A tool is disclosed. Further, Patent Document 4 discloses an invention that stabilizes heat dissipation performance by providing ring-shaped irregularities on the outer surface of the nozzle. Moreover, in patent document 5 and patent document 6, by forming a groove | channel and unevenness | corrugation of depth 0.5-50 micrometers in a nozzle outer surface, the glass long fiber which generate | occur | produces by the oozing to the nozzle outer surface of molten glass is carried out. An invention for preventing cutting is also disclosed. Patent Document 7 discloses a bushing for producing glass fibers comprising at least one layer in which the composition ratio of ceramics and noble metal is changed in stages on a chip plate of the bushing in order to prevent volatilization of the noble metal.

JP 2000-335932 A JP 2000-344541 A Japanese Patent Laid-Open No. 02-097433 Japanese Patent Laid-Open No. 02-153837 Japanese Patent Laid-Open No. 04-083730 Japanese Patent Laid-Open No. 04-083731 Japanese Patent Laid-Open No. 06-298543

  However, in spite of the fact that the inventions listed above are not sufficient, it is a fact that long glass fibers are widely used in various applications. In recent years, by managing the fiber diameter of the long glass fiber with higher accuracy than before, when the long glass fiber is molded for use as a composite material, the strength of the composite material is high. It has been found that stable performance can be realized, and a long glass fiber having a higher precision than before has been required for many applications. Therefore, research on the most suitable bushing has been conducted in order to produce a long glass fiber having such high-precision dimensions. The problem here is various causes that affect the glass fiber diameter, but the diameter of the long glass fiber is not simply determined by the dimensional accuracy of the hole diameter of the nozzle opening, but at high temperatures. This is influenced by various factors such as the time-dependent deformation of the glass, the evaporation of the material constituting the bushing, and the temperature, speed and atmosphere when the long glass fiber is drawn. For this reason, it is necessary to study and improve these factors one by one. The inventors of the present invention have made researches to improve such problems, and as described in Patent Document 7, in order to adjust the fiber length of the long glass fiber to be highly accurate, the structure of the nozzle It is often the case that improvements are made in terms of dimensions and dimensions, but it is found that there are other drastic improvements, that is, it is better to focus on the bushing plate part other than the nozzle. The idea is disclosed.

  The present invention is capable of forming or spinning glass long fibers having a high-precision fiber diameter in a high temperature state over a long period of time by reducing the amount of evaporates resulting from bushing at high temperature and strengthening the bushing. It is an object of the present invention to make it possible to produce excellent long glass fibers for composite materials.

  In order to solve the above-mentioned problems, the bushing for producing long glass fiber according to the present invention has a bushing body having a molten glass supply space inside, a bushing peripheral wall portion, and a bushing plate disposed on the bottom portion thereof. A bushing for producing glass long fibers, wherein a plurality of nozzles are provided on the bottom side of the bushing plate to allow the molten glass from the molten glass supply space to flow out in order to form the long glass fibers. The coating is not formed in a region near the nozzle that is 1 mm or more away from the position corresponding to the boundary with the nozzle on the outer surface of the bushing plate, and the coating is applied to a region other than the region near the nozzle on the outer surface of the bushing plate. As the film is formed, the coating is made of ceramics, glass ceramics and glass materials. Characterized in that it is any coating using one or more.

  According to such a configuration, the region other than the region in the vicinity of the nozzle on the outer surface of the bushing plate constituting the bushing body of the long glass fiber manufacturing bushing is either ceramics, glass ceramics (also referred to as crystallized glass), or glass. The outer peripheral surface and end surface of the nozzle attached to the bottom surface side of the bushing plate, and the bushing plate, while being coated by a structural material containing such a material so as to have a film-like appearance The area in the vicinity of the nozzle on the outer surface is not covered with such a coating.

  Explaining the circumstances that led to the adoption of such a configuration, the present inventors investigated the evaporation of the bushing material from the outer surface of the glass long fiber manufacturing bushing, and it was not necessarily the evaporation from the nozzle alone. Rather, it was found that evaporation from the surrounding bushing plate was greatly involved. In addition, the nozzle itself has been able to take appropriate countermeasures due to various improvements so far, but it has also become clear that there are no countermeasures at other points. Therefore, the present inventors coated the bushing plate material from the outer surface of the bushing plate by coating a specific portion of the surface of the bushing plate, not the nozzle, with a selected heat-resistant material. Attention was paid to the fact that the bushing for manufacturing long glass fibers that prevents evaporation over time in a high temperature environment and is exposed to a high temperature state for a long time can maintain a stable state and performance for a long time.

  The area of the outer surface of the bushing plate on which the coating using any one or more of the above material groups is formed does not necessarily have to cover the entire surface, except for the outer peripheral surface and end surface of the nozzle and the vicinity of the nozzle. In addition, it is preferable that at least 20% or more of the area of the exposed surface to the outside of the bushing plate is covered. In addition, the covered part does not need to be a continuous surface, and does not need to be gathered at one place. It is preferable that only the easy-to-use portions can be efficiently covered. Here, the above-mentioned “at least 20% or more essential region” means an outer surface that is particularly likely to be in a high temperature state, an outer surface that is weak in structure due to the action of a tensile force, or the most evaporated. Is an outer surface satisfying any condition of the outer surface that is known to be severe. Such an outer surface can be obtained by a structural simulation model, or may be obtained by actual measurement such as temperature measurement.

  Here, the material of the bushing plate, the material of the nozzle, and the attachment structure of the nozzle to the bushing plate are not particularly limited as long as they have the ability to continuously and stably draw out the molten glass in a high temperature state. Also, there is no particular limitation on the method of applying a coating material made of one or more of ceramics, glass ceramics or glass.

  Further, the external shape and dimensions of the nozzle and bushing plate are not particularly limited. For example, the nozzle shape may be a cylindrical shape, a polygonal cylindrical shape, a frustum-shaped outer shape, a dome-shaped outer shape, or the like, and one or more of ceramics, glass ceramics, or glass is used for the outer surface. A predetermined groove, unevenness, dimple, protrusion, or the like can be provided at a predetermined interval or randomly so that a film different from the formed film can be easily formed. Further, the surface state of the outer surface can be changed to a surface state having fine undulations by physical means such as sand blasting or various chemical treatments such as acid and alkali. Further, the bushing plate is not necessarily flat, and may be in a state of being provided with irregularities, grooves, or the like, and the entire bushing plate may be curved.

  As for the arrangement positions of the multiple nozzles of the bushing plate, it does not matter whether the nozzles are arranged in any position. For example, the unit arrangement of a large number of nozzles may be such that three nozzle positions are arranged in a triangle, or four nozzle positions are arranged in a substantially rectangular shape. A combination of both, or a completely different arrangement may be used.

  In the above configuration, the outer peripheral surface and end surface of the nozzle and the outer surface of the bushing plate excluding the nozzle vicinity region are coated with an appropriate material as described above. It does not intentionally exclude the outer peripheral surface and end surface and the vicinity of the nozzle. For example, the outer peripheral surface and end surface of the nozzle and the vicinity of the nozzle can sufficiently avoid the influence on the glass fiber drawn in the molten state. In addition, if it is more effective to form a film in such a place, it does not prevent the formation of a film made of a material different from the film described above. However, when such a film is formed, it is better to avoid it when it is judged that it is easy to peel off.

  On the other hand, the bushing for producing long glass fibers according to the present invention includes a bushing main body in addition to the outer surface of the bushing plate as a portion for forming a coating using any one or more of ceramics, glass ceramics, and glass material groups. The outer surface of the peripheral wall portion of the bushing, which is a constituent element, may also be the target. Also in this case, the above-mentioned film may be formed on the entire area of the outer surface of the bushing peripheral wall portion, or the above-mentioned film may be formed on an appropriate partial area, for example, a partial area connected to the bushing plate. . In addition, for example, a coating can be formed on the surface of a construction part such as a cooling pipe or a fin, a terminal, a reinforcing member of a bushing plate, etc., but the coating formed at such a location is the outer surface of the bushing plate. May be of the same material and thickness, or may be of a different structure.

  In addition, as for the formation method of the film, if the place where the film is to be formed is only a specific limited part, the outer surface of the place where the film is not formed is previously covered with an organic material or other masking material. It is also possible to apply the film formation in the covered state, and then remove the masking by a predetermined method so that the film is selectively formed. Or a predetermined assembly process of a bushing plate may be performed first as needed, and a film may be formed only on a desired member in the middle.

  On the other hand, if the bushing plate made of a platinum alloy or platinum is used for the long glass fiber manufacturing bushing according to the present invention, high performance is maintained with respect to high heat resistance and low reactivity at high temperatures with molten glass. Therefore, not only the outer surface of the bushing plate but also the change over time of the inner surface can be reduced, and since the deterioration of the inner surface is small, it is possible to efficiently produce long glass fibers.

  Here, the bushing plate made of a platinum alloy or platinum means that the material constituting the bushing plate is platinum, that is, platinum, rhodium, iridium, yttrium, ruthenium, palladium, osmium, titanium, gold, molybdenum, tungsten, An appropriate amount of magnesium, calcium, hafnium, zirconium, or the like may be contained, and the content of these coexisting components is not particularly limited as long as a predetermined performance such as heat resistance can be realized. It goes without saying that platinum alloys and materials other than platinum can be used together in order to achieve a desired effect. In addition, the material of the bushing plate according to the present invention is not limited to a solid solution alloy as a platinum alloy, but a cermet in which fine particles are dispersed in platinum or a cermet solidified by adding a ceramic material. It may be in a shape.

  In addition, the bushing for producing long glass fiber according to the present invention has a multi-layered coating, and the outer surface and the bushing plate (or the bushing plate (or the like) are adjusted by adjusting various physical properties such as an expansion coefficient and heat resistance within a desired range. In addition to this, it is possible to select materials that are easily adaptable to the interface with the bushing peripheral wall portion), and it is possible to obtain an optimum configuration required for the bushing plate.

  Here, the coating film having a multilayer structure means that the coating film is composed of two or more layers by a plurality of film forming operations.

  About the thickness dimension, component, etc. of each layer which comprises the film of a multilayer structure, it can select so that it may become a preferable component and structure as needed (however, 1 or more of ceramics, glass ceramics, or glass) Limited to coatings using Further, each layer does not need to be uniform, and may have an inclined structure or a stitch structure. Moreover, arbitrary aggregates can also be intentionally added to the components constituting the layer. As the aggregate, those preferable in terms of heat resistance, expansion coefficient or reactivity can be used. For example, glass filler, ceramic filler, glass ceramic filler, noble metal filler, etc. can be used in appropriate amounts. Any filler shape can be selected. For example, approximately fiber shape, approximately cotton shape, approximately mesh shape, approximately braided shape, approximately balloon shape, approximately microbead shape, approximately crushed material shape, approximately porous body shape, approximately polyhedral shape, approximately columnar shape, approximately polygonal column shape, approximately plate Shape, substantially pellet shape, substantially conical shape, substantially polygonal shape, or substantially alphabetical columnar shape can be used.

  Further, when the coating has a multilayer structure, higher performance can be realized by assigning a function specific to each layer. For example, on the bushing plate surface, a layer with an emphasis on bonding with a bushing plate material such as platinum alloy or platinum is disposed, and a dense layer is disposed above this layer to suppress evaporation from the bushing plate. Alternatively, a layer having a dense structure may be provided on the bushing plate surface itself, and a layer with high heat resistance that does not easily fall off may be employed as an upper layer. In addition, for example, a layer to which a specific filler is added is arranged so that the thermal expansion coefficient changes gradually to suppress the generation of cracks, and furthermore, the upper layer has heat resistance and at the same time efficiently prevents evaporation from the bushing plate surface. Such noble metal fillers can also be employed.

  Moreover, although the heat-resistant temperature of a film is dependent also on the construction method and the kind of construction material, it needs to have the heat resistance of at least 800 degreeC or more, More preferably, it is 1000 degreeC, More preferably, it is 1200 degreeC. It has the above heat resistance. In order to realize such heat resistance, it is preferable to perform firing at a temperature higher than that.

  Further, the bushing for producing a glass long fiber according to the present invention, if the coating is any one of a preform coating, a spray coating, a dipping coating, and a vapor deposition coating, by selecting a coating suitable for the bushing plate material, An optimum configuration can be obtained, and a high-quality film can be applied economically and inexpensively.

  Here, the coating is any one of a preform coating, a spray coating, a dipping coating, and a vapor deposition coating. The coating applied to the outer surface of the bushing plate excluding the nozzle outer peripheral surface and the nozzle end surface depends on the preform. Either formed in advance or formed by injection using a spray device, or formed by immersing the work surface of the bushing plate in a pre-adjusted dipping paste Or formed by adopting a physical or chemical vapor deposition method.

  Regarding these film forming methods, one method may be adopted or a plurality of methods may be used in combination. There is no problem with combining these methods with other film forming methods.

  In addition to the above, the bushing for a long glass fiber manufacturing apparatus according to the present invention is preferably a coating having a thickness of 1 mm or less because the coating has a stable structure over a long period of time.

  Here, the thickness of the coating being 1 mm or less means that the thickness of the coating is measured at the time of construction or after the construction, and the measured value of the thickest portion is 1 mm or less.

  The reason why the thickness dimension of the coating is controlled to 1 mm or less is as follows. The first reason is that when the thickness of the thin film exceeds 1 mm, peeling between the construction surface and the coating after drying tends to occur. The bushing plate is made of a platinum alloy or platinum as described above, and the thickness of the platinum alloy or platinum is 2 mm or less in consideration of the manufacturing cost of the bushing for producing long glass fibers. The outer peripheral surface and end face of the bushing for producing glass long fibers and the outer surface of the bushing plate excluding the vicinity of the nozzle are covered with a coating using one or more of ceramics, glass ceramics, and a glass material group. When the film thickness of the film becomes 1 mm or more, the dry film becomes a rigid dry film that does not cause deformation. As a result, when the platinum alloy or platinum, which is the construction surface, undergoes some deformation during construction, the dry film cannot follow the deformation, and there is a high risk of delamination. The second is due to the occurrence of firing shrinkage when a rigid dry film of 1 mm or more is fired. A film with low density can suppress firing shrinkage, but a film with high density is indispensable for a film that prevents volatilization of platinum. The density of the film can be determined by measuring the porosity. When the porosity is 10% or more, it is difficult to suppress platinum volatilization, and desirably 5% or less is required. Increasing the density increases firing shrinkage, and if the film thickness is 1 mm or more, the risk of cracking of the film during firing increases. Therefore, the thickness dimension of the coating is preferably 1 mm or less as the total thickness of the layer, more preferably 800 μm or less, still more preferably 600 μm or less, and even more preferably 400 μm or less. It is.

  As the glass fiber that can be produced by the bushing for producing long glass fiber according to the present invention, any known glass long fiber made of glass can be produced. For example, E glass (non-alkali glass composition), AR glass (alkali resistant glass composition), C glass (acid-resistant alkali lime-containing glass composition), D glass (composition realizing low dielectric constant), S glass (high strength) , T glass (composition realizing high strength and high elastic modulus) and H glass (composition realizing high dielectric constant), or glass materials such as M glass and L glass. Even other materials can be used.

  On the other hand, the method for producing a bushing for producing glass long fibers according to the present invention comprises a bushing body forming step of assembling a bushing body comprising a bushing peripheral wall, a bushing plate, and a number of nozzles, and an outer peripheral surface of the nozzle in the assembled bushing body When the coating is formed on at least the outer surface of the bushing plate excluding the end face, the coating is not formed on the outer surface of the bushing plate without forming a coating in a region near the nozzle that is 1 mm or more away from the position corresponding to the boundary with the nozzle on the outer surface. A coating process for forming a coating film in a region other than the nozzle vicinity region on the surface, and forming a coating film using any one or more of ceramic, glass ceramics, and glass material group as the coating film, and a formed coating film And a baking process that heats to a dense structure. It is intended to produce a long glass fiber production bushing according to any of the above.

  As for the bushing body formation process, the bushing peripheral wall, bushing plate, and many nozzles may be assembled so that the basic structure of the bushing for manufacturing long glass fibers described above is obtained, and the assembly procedure is performed at an optimum efficiency. It is preferable to set so that a high quality structure can be obtained. For example, all the nozzles may be preferentially attached to the bushing plate first, and conversely, the nozzles may be attached last. As a method for attaching the nozzle, various known methods may be employed.

  Also, as described above, various methods should be adopted for the coating process for forming a coating on the outer surface of at least the bushing plate (that is, the bushing plate alone or the bushing plate and the bushing peripheral wall) of the assembled bushing body. Therefore, it is sufficient that a bushing having a stable quality can be configured.

  Regarding the firing step of heating the formed film so as to have a dense structure, in order to make the film have sufficient durability at the temperature at which the glass fiber is drawn out by the bushing for producing long glass fiber, By heating the film to a temperature at which it is drawn, the film can be brought into a state of being firmly bonded to the bushing surface.

  The heating means used in the firing step may be a means for applying a local heating means or a means for heating the entire bushing, and is maintained at an appropriate temperature in an electric furnace or various fuel heating furnaces. The glass long fiber manufacturing bushing may be disposed in the glass melting furnace and then heated by a heating source of the glass melting furnace.

  About the heating temperature in a baking process, it is preferable to heat in the range of 1100 to 1500 degreeC. That is, when the bushing for producing long glass fiber is heated at a temperature lower than 1100 ° C., there is a risk that the entire heating becomes insufficient, or there is a problem that a portion where heating cannot be performed uniformly occurs. This is not preferable. On the other hand, heating at a temperature exceeding 1500 ° C. is not preferable because thermal energy that is overloaded is imparted to the coating, which may shorten the useful life of the coating. From the above viewpoint, in order to obtain a more stable coating film, the heating temperature in the firing step is more preferably in the range of 1200 ° C to 1400 ° C.

  The long glass fiber manufacturing apparatus according to the present invention is characterized in that the glass long fiber is spun using any one of the long glass fiber manufacturing bushings described above.

  It does not specifically limit about the form of the glass long fiber product using the glass filament (glass long fiber) manufactured with this glass long fiber manufacturing apparatus. That is, as a form of the glass fiber product, yarn, roving, DWR (direct winding roving), chopped strand, milled fiber, cloth, mat, tape, braided cloth, or the like is possible.

  In this long glass fiber manufacturing apparatus, in addition to the above, various incidental facilities or jigs can be appropriately provided and used. For example, a cooling device or jig such as a glass fiber cooling pipe or fin, a device that intentionally adjusts the oxidation-reduction atmosphere around the bushing plate, a cooling medium spraying device for cooling, a temperature control device for the bushing plate, etc. is there. These devices and jigs may be used alone or in combination, and do not hinder the use of other devices.

  On the other hand, the method for producing a long glass fiber according to the present invention is characterized in that the long glass fiber for a composite material is produced while monitoring the outer surface of the bushing plate and the spinning state using the above glass long fiber production apparatus. And

  A specific example for producing a long glass fiber for a composite material while monitoring the outer surface of the bushing plate and the spinning state using the above long glass fiber manufacturing apparatus will be described. By arranging in a glass melting furnace for melting molten glass, the molten glass that has flowed out of the glass melting furnace is guided into the glass long fiber manufacturing apparatus, and continuously from the nozzle attached to the bushing plate of the glass long fiber manufacturing apparatus. When producing the glass fiber by drawing it out, the production is performed while monitoring whether the glass fiber is smoothly drawn out and spun smoothly outside the bushing plate. This is because the bushing plate can be observed at the same time as observing the glass fiber, and if any measures are required, for example, if foreign matter adheres to the outer surface or fragile parts occur, the necessary corrections are necessary. It can be dealt with promptly by treatment.

  Here, various methods can be adopted as a method for monitoring the outer surface of the bushing plate and the spinning state of the long glass fibers. For example, as a digital or analog image as a moving image of the outer surface of the bushing plate and spinning status or an intermittent still image via a wired or wireless intranet line via an imaging device equipped with a solid-state imaging device such as an imaging tube or CCD or CMOS. It is also possible to transmit information to a monitoring device and monitor it, and to measure the dimensional fluctuation and temperature fluctuation at a predetermined point that requires attention by electronic recording system of visible light and other electromagnetic waves instead of images, and display the value It is also possible to monitor via visual observation or a monitoring program while accumulating on the top, recording paper, or recording medium.

  In addition, the method for producing a long glass fiber according to the present invention provides a glass long fiber product suitable for various uses from the beginning if the glass long fiber for composite material is any one of FRP, FRTP and GRC. High quality can be achieved over a long period of time, and the production cost can be reduced by improving the production efficiency.

  In this case, if the long glass fiber for composite material is any of FRP, FRTP, and GRC, the long glass fiber for composite material may be a thermosetting resin reinforced body (also referred to as FRP) or thermosoftening property. It can be used as a glass long fiber product constituting a cured resin (also referred to as FRP) or an alkali-resistant glass fiber reinforced cement product (also referred to as GC).

  When configuring these long glass fibers for composite materials, what is selected as a component other than the mixing ratio and mixing method of the glass fibers for composite materials according to the present invention, and further, the glass fibers for composite materials according to the present invention As for, any material can be added as long as it can realize desired performance such as mechanical strength, chemical durability, heat resistance, chemical resistance or weather resistance. .

  Moreover, in the manufacturing method of the long glass fiber which concerns on this invention, various surface coating agents can be apply | coated with various methods with respect to the surface of the glass fiber just under a bushing. For example, a sizing agent, an antistatic agent, a surfactant, a polymerization initiator, a polymerization inhibitor, an antioxidant, a film forming agent, a coupling agent, or a lubricant may be coated, and a water reducing agent as necessary. , Fluidizer, thickener, waterproofing agent, rust preventive agent, curing accelerator, curing retarder, slag, fly ash, silica fume, colorant or rapid setting agent may be mixed.

  In addition, the glass fiber manufactured with the manufacturing method of the glass long fiber which concerns on this invention is not specifically limited about the fiber diameter and fiber cross-sectional shape of the monofilament which comprises a strand. That is, monofilament glass fibers having a diameter of several μm to several tens of μm can be used, and a true circle, a substantially ellipse, a flat circle, a hollow circle, a substantially rectangular shape, or the like can be appropriately employed for the cross-sectional shape. .

  Moreover, the glass fiber product manufactured with the manufacturing method of the long glass fiber which concerns on this invention may be specifically used for the following various uses, for example. For example, in automotive applications, body roofing materials (roof materials), window frame materials, vehicle body fronts, car bodies, lamp houses, air spoilers, fender grills, tank trolleys, ventilators, water tanks, waste tanks, seats, nose cones, There are fender grille, curtains, filters, air conditioner ducts, muffler filters, dash panels, fan blades, radiator tires, timing belts, etc. For electronic equipment related applications, for electronic equipment housing materials, gear tape reels, various storage cases, optical parts There are packages, packages for electronic components, switch boxes or insulating supports, etc. For aircraft-related applications, engine covers, air ducts, seat frames, containers, curtains, interior materials, service trays, tires, anti-vibration materials or There are imming belts, etc., for shipbuilding, land shipping and shipping related applications, motor boats, yachts, fishing boats, domes, buoys, marine containers, floaters, tanks, traffic lights, road signs, curve mirrors, containers, pallets, guardrails, light cover or spark protection There are seats, etc., in construction, civil engineering and building materials related, bathtubs, bath toilet units, toilets, septic tanks, water tanks, interior panels, capsules, valves, knobs, wall reinforcement, precast concrete boards, flat plates, corrugated plates, tents, There are shutters, exterior panels, sashes, piping pipes, reservoirs, pools, roads, structure side walls, concrete formwork, tarpaulins, waterproof linings, curing sheets or insect screens, etc. for agricultural applications, greenhouses, silo tanks, spray nozzles , Struts, linings or For industrial facilities, there are bug filters, sewer pipes, water purification equipment, anti-vibration concrete reinforcement (GRC), water tanks, belts, chemical tanks, reaction tanks, containers, fans, ducts, corrosion resistance There are linings, valves, refrigerators, trays, freezers, troughs, equipment parts, motor covers, insulation wires, transformer insulation, cable cords, work clothes, curtains, evaporation panels or equipment housings, etc. There are skis, archery, golf clubs, pools, canoes, surfboards, camera housings, helmets, shock protection armor, flower pots or display boards. For daily necessities, tables, chairs, beds, benches, mannequins, trash cans or mobile terminals There are protective materials.

  The method for producing long glass fibers according to the present invention is characterized in that the monitoring of the spinning state is based on any one or more of taking a spinning image, measuring the spinning speed, and measuring the fiber diameter.

  According to such a configuration, the photographing of the image showing the state of the outer surface of the glass fiber continuously drawn from the nozzle of the bushing for producing long glass fibers, the drawing speed of the glass fiber from the nozzle, and each glass The spinning status can be monitored by any investigation of the measurement of the fiber diameter of the long fibers.

  The spinning image may be photographed by photographing a plurality of glass fiber bundles at the same time, or by photographing a predetermined number of monofilaments with separate photographing devices. If it is obtained, preferable conditions can be selected for the resolution, imaging frequency, and the like in accordance with the imaging environment and the imaging equipment.

  (1) As described above, the bushing for producing long glass fibers according to the present invention is configured to flow out molten glass from a large number of nozzles attached to the bushing plate to form long glass fibers (glass filaments). In addition, the outer surface of the bushing plate except for the outer peripheral surface and end surface of the nozzle and the vicinity of the nozzle (including the outer surface of the peripheral wall portion of the bushing in some cases) may be any one of ceramics, glass ceramics, and a glass material group. Since a film using one or more is formed, the amount of evaporant generated from the outer surface of the bushing during the production of the long glass fiber is suppressed, and the bushing is strongly reinforced. Therefore, high productivity can be realized in the production of glass fibers used for various applications.

  (2) Furthermore, the bushing for producing long glass fibers according to the present invention has a high heat resistance if the bushing plate is made of a platinum alloy or platinum. Therefore, it is possible to manufacture a highly accurate glass fiber having high dimensional stability.

  (3) Further, the bushing for producing long glass fibers of the present invention can have various performances required for the outer surface of the bushing in each layer structure of the coating if the coating has a multilayer structure. Since the performance required for the layer is relaxed, a stable layer structure can be easily formed.

  (4) Further, the bushing for producing long glass fiber according to the present invention has the structure, dimensions and surface state of the bushing plate if the coating is any one of a preform coating, a spray coating, a dipping coating and a vapor deposition coating. An optimal film can be formed by a suitable film forming method. The coating method can also be selected depending on the type of coating material.

  (5) In addition, the bushing for a long glass fiber manufacturing apparatus of the present invention has a strong structure integrated with the bushing plate so that the coating is difficult to crack or peel off if the thickness of the coating is 1 mm or less. Therefore, it can be used for a long time.

  (6) A method for producing a bushing for producing long glass fibers according to the present invention comprises: a bushing body forming step of assembling a bushing body comprising a bushing peripheral wall, a bushing plate, and a number of nozzles; and an outer periphery of the nozzle in the assembled bushing body Since it has a coating process for forming a film on at least the outer surface of the bushing plate excluding the surface and end face and the nozzle vicinity region, and a firing process for heating the formed film to have a dense structure, A dense coating can be formed in a continuous state on the outer surface of the bushing for producing long glass fibers, and it is possible to reliably suppress evaporation from the outer surface of the bushing, so that dimensional stability is improved. Manufacture of long glass fiber that can realize improvement of glass quality such as realization and suppression of foreign matter generation It is possible to obtain a bushing.

  (7) Since the apparatus for producing long glass fibers of the present invention is constructed so as to spin the long glass fibers using the above-mentioned bushing for producing glass fibers, various glass long fibers having excellent quality. You can get a product.

  (8) The method for producing a long glass fiber of the present invention is to produce a long glass fiber for a composite material while monitoring the outer surface of the bushing plate and the spinning state using the above-described long glass fiber production apparatus. Thus, stable and efficient production can be maintained, and defects generated in the glass fiber product due to foreign matters and the like can be suppressed to a minimum.

  (9) Further, the method for producing a long glass fiber of the present invention is excellent in glass fiber reinforced products for various uses required from the market if the glass fiber for composite material is any one of FRP, FRTP and GRC applications. It can be supplied to lubrication without delay in quality.

  (10) The method for producing a long glass fiber of the present invention may occur during glass production if the spinning status is monitored by any one or more of taking a spinning image, measuring a spinning speed, and measuring a fiber diameter. It is easy to obtain information for taking measures to minimize the various problems that occur, and glass fibers that are in the most stable state by promptly taking appropriate measures Quality can be maintained for a long time.

It is a perspective view which shows embodiment of the bushing which the glass long fiber manufacturing apparatus which concerns on this invention comprises. It is a bottom view which shows embodiment of the bushing which the glass long fiber manufacturing apparatus which concerns on this invention comprises. It is a principal part expansion vertical front view which shows embodiment of the bushing which the glass long fiber manufacturing apparatus which concerns on this invention comprises.

  Hereinafter, embodiments of a bushing for producing long glass fibers (hereinafter simply referred to as a bushing) according to the present invention will be described with reference to the drawings.

  1 to 3 exemplify a bushing 1 included in a glass long fiber manufacturing apparatus. FIG. 1 is a perspective view showing a main part of the bushing 1, and FIG. 2 shows a main part of the bushing 1. FIG. 3 is a bottom view, and FIG. 3 is an enlarged vertical front view showing only the periphery of the nozzle of the bushing 1. As shown in FIGS. 1 and 2, the bushing 1 is used when molding (or spinning) a glass long fiber having an E glass composition used for FRP applications. And the bushing main body 2 of this bushing 1 is comprised by fixing the bushing plate 4 to the bottom part of the bushing surrounding wall part 3, The inside is made into the molten glass supply space 5 (refer FIG. 3). More specifically, the bushing plate 4 is made of a platinum rhodium alloy having a substantially rectangular shape, and 2000 heat-resistant nozzles 6 are attached to the bottom surface of the bushing plate 4 and the inner peripheral surface of the bottom end portion of the bushing peripheral wall portion 3. The outer peripheral end surface of the bushing plate 4 is joined by TIG welding.

  Then, the outer surface of the bushing plate 4 and the outer surface of the bushing peripheral wall 3 are composed of two layers in a portion corresponding to 40% of the total area (the portion with cross-hatching in FIGS. 1 and 2). A film 7 is formed. The two-layer coating 7 has a heat resistance of 1300 ° C., and the dense layer corresponding to the first layer is a mixture of a non-alkali glass powder composition with silica fine powder and alumina powder. A dense layer structure capable of efficiently shielding the evaporation of platinum and rhodium from the bushing plate 4 has a thickness dimension of 200 μm. The heat-resistant and high-strength layer corresponding to the second layer of the coating 7 is a composite constituent layer containing ceramic fibers and also containing non-alkali glass powder, and the thickness dimension of the layer is 100 μm. This heat-resistant and high-strength layer is blended so as to suppress cracking of the coating surface. The two-layer coating 7 applied to the bushing plate has a thickness of 300 μm in total for the first and second layers.

  As for the portion where the coating film 7 having the two-layer structure is formed, avoid the end surface of the nozzle 6 made of platinum rhodium alloy, the outer peripheral surface thereof, and the vicinity of the nozzle 6 on the outer surface of the bushing plate 4. From the position corresponding to the boundary with the nozzle 6 on the outer surface to a portion having a dimension of 1 mm or more, the formation of the coating 7 is avoided, and the other outer surfaces of the bushing plate 4 and the outer surface of the bushing peripheral wall 3 are determined. The film 7 is formed in the place. The coating film 7 is formed in such a manner that the evaporated material from these locations is cooled by fins (not shown) and cooling pipes (not shown) around the bushing plate 4 in the previous investigations. This is because it has been found that accumulation in the vicinity of 6 may adversely affect the molding of the glass fiber F. Further, when the coating film 7 is formed on the end surface of the tip of the nozzle 6, even if there is no problem at the beginning of production, in the production of the long glass fiber F over a long period of time, a part of the coating film 7 becomes the long glass fiber F for some reason. This is because there is a possibility that thread breakage may occur in the glass fiber F due to adhesion.

  The first layer of the coating 7 is formed by spray coating the portion where the coating is not applied with a masking tape such as an organic film, and the second layer is sprayed from above the first layer. It is formed by spraying.

  The manufacturing procedure of the bushing 1 having the above-described configuration is as follows. First, the bushing plate 4 having the nozzle 6 attached thereto is welded to the bushing peripheral wall portion 3 and the bushing body 2 is assembled. A coating process is performed in which the coating film 7 is formed on the main body 2 in a portion corresponding to 40% of the total area of the outer surface of the bushing plate 4 and the bushing peripheral wall portion 3 so as to have the above-described two-layer structure. Next, after the bushing 1 in a state where the coating film 7 is formed is incorporated into the long glass fiber manufacturing apparatus, the bushing 1 is used until a high temperature state of 1300 ° C. is obtained using a heating device attached to the glass fiber manufacturing apparatus. By heating uniformly, a coating structure having high stability can be obtained through a baking step for densifying the entire coating 7 and improving adhesion.

  Next, a method for producing glass long fibers having an E glass composition for FRP using a glass long fiber production apparatus including the bushing 10 having the above-described configuration will be described.

  First, a glass raw material prepared to have an E glass composition is charged into a glass melting furnace using a raw material charging machine. The glass raw material thus charged is heated to 1300 ° C. or higher by a heating source such as electricity or fuel gas in a glass melting tank to cause a vitrification reaction, and a heterogeneous rough melting in which many reactive bubbles are involved. It becomes a molten glass in a state. This coarse molten glass is adjusted to become a molten glass G in a homogeneous state by a series of homogenization operations such as clarification and stirring, and then the homogeneous molten glass G passes through the fore bay of the glass melting furnace, and then a bushing. 1 flows into the molten glass supply space 5.

  Then, the molten glass G that has flowed into the molten glass supply space 5 of the bushing 1 stays in the molten glass supply space 5 and then is attached to the bushing plate 4 adjusted to an appropriate temperature by a heating device or the like. The glass filament F having a diameter of several μm to several tens of μm is obtained by being continuously drawn out as a thin stream of molten glass without interruption from the opening hole at the tip of the nozzle 6 having the above heat resistance. Here, the spinning condition (molding condition) of the glass filament F directly below the nozzle 6 and the outer surface condition of the bushing plate 4 are visually monitored by a regular dedicated monitor, and a part of the condition is checked by a CCD camera. The photographed image can be monitored as necessary in another monitoring room by a factory LAN. By such a monitoring system, when a problem occurs in the glass filament (glass monofilament) F that is continuously drawn, it is possible to take measures sequentially. In addition, the image from the CCD camera can be recorded as required, and can be used for high-quality molding.

  The glass filament F drawn out from the nozzle 6 is rapidly reduced in temperature by a cooling fin or a cooling pipe directly under the nozzle 6 to become a glass fiber having an E glass composition, and various sizing agents such as a silane coupling agent and starch are added to the glass filament F. A strand in which dozens to thousands are bundled by coating on the surface is formed, and this is wound around a paper tube to form a cake (also referred to as roving) or cheese.

  Then, it can respond | correspond by further processing a glass long fiber to various glass long fiber products as needed with a glass long fiber manufacturing apparatus. For example, in the case of glass roving, a plurality of strands after drying are unwound and aligned while applying a twill, wound using a winder having a winder, and wound (roll) Or a shape called a wound body).

  As described above, when glass fibers for various uses are manufactured using the long glass fiber manufacturing apparatus including the bushing 1, the evaporation from the bushing plate 4 is efficiently suppressed, and the bushing plate 4 itself is further suppressed. Because it is possible to maintain high strength, the lifetime of glass fiber manufacturing equipment will be longer than before, enabling efficient production, and for composite materials with stable performance and superior performance. It becomes possible to produce various types of long glass fibers.

  The bushing and long glass fiber manufacturing apparatus according to the present invention and the long glass fiber manufacturing method using them are also used for manufacturing long glass fibers used in other applications in addition to the use in composite materials such as FRP. It can be applied and can be used in a wide range of fields. Moreover, if it manufactures using the manufacturing apparatus of the form similar to the glass fiber manufacturing apparatus based on this invention, even if it is another glass material, it is possible to apply this invention.

DESCRIPTION OF SYMBOLS 1 Bushing for glass long fiber manufacture 2 Bushing main body 3 Bushing peripheral wall part 4 Bushing plate 5 Molten glass supply space 6 Nozzle 7 Coating G Molten glass F Glass long fiber (glass filament)

In order to solve the above-mentioned problems, the bushing for producing long glass fiber according to the present invention has a bushing body having a molten glass supply space inside, a bushing peripheral wall portion, and a bushing plate disposed on the bottom portion thereof. A bushing for producing glass long fibers, wherein a plurality of nozzles are provided on the bottom side of the bushing plate to allow the molten glass from the molten glass supply space to flow out in order to form the long glass fibers. there are, without forming a film on the outer peripheral surface and the end face of the nozzle, and, the coating nozzle area near the position corresponding to the boundary between the nozzle to a position spaced above 1mm on the outer surface of the bushing plate formed without the co-when forming the film in a region other than the nozzle area near the outer surface of the bushing plate , Said coating, ceramics, characterized in that a coating with any one or more of the material group glass ceramics and glass.

On the other hand, the method for producing a bushing for producing long glass fibers according to the present invention comprises a bushing body forming step for assembling a bushing body comprising a bushing peripheral wall portion, a bushing plate and a number of nozzles, and an outer peripheral surface of the nozzle in the assembled bushing body. and when forming a film on the outer surface of at least the bushing plate to the exclusion of the end surface, without forming the film on the nozzle area near the position corresponding to the boundary between the nozzle to a position spaced above 1mm in outer surface , coatings formed while forming the film in a region other than the nozzle area near the outer surface of the bushing plate, as the film, ceramics, coatings with any one or more of the material group glass ceramics and glass a step, the formed the coating and dense structure And a firing step of heating so that is intended to produce a long glass fiber production bushing according to any of the above.

Claims (11)

A bushing body having a molten glass supply space formed therein includes a bushing peripheral wall portion and a bushing plate disposed on the bottom portion thereof, and for molding long glass fibers on the bottom surface side of the bushing plate. A glass long fiber manufacturing bushing provided with a plurality of nozzles for allowing the molten glass to flow out from the molten glass supply space,
A film is not formed in a region near the nozzle that is 1 mm or more away from a position corresponding to the boundary with the nozzle on the outer surface of the bushing plate, and a film is formed in a region other than the region near the nozzle on the outer surface of the bushing plate. A bushing for producing long glass fibers, wherein the coating is a coating using any one or more of ceramics, glass ceramics, and glass material groups.   The bushing for producing long glass fibers according to claim 1, wherein the coating is formed on the outer surface of the peripheral wall portion of the bushing.   The said bushing plate consists of platinum alloys or platinum, The bushing for glass long fiber manufacture of Claim 1 or 2 characterized by the above-mentioned.   The said coating film is a multilayer structure, The bushing for glass long fiber manufacture in any one of Claims 1-3 characterized by the above-mentioned.   The bushing for producing long glass fibers according to any one of claims 1 to 4, wherein the coating is any one of a preform coating, a spray coating, a dipping coating, and a vapor deposition coating.   The bushing for producing glass long fibers according to any one of claims 1 to 5, wherein the coating has a thickness of 1 mm or less. It is a manufacturing method which manufactures the bushing for glass long fiber manufacture in any one of Claims 1-6,
A bushing body forming step of assembling a bushing body comprising the bushing peripheral wall portion, a bushing plate, and a number of nozzles;
When forming a coating on at least the outer surface of the bushing plate excluding the outer peripheral surface and end surface of the nozzle in the assembled bushing body, in the vicinity of the nozzle at a distance of 1 mm or more from the position corresponding to the boundary with the nozzle on the outer surface. A film that does not form a film and forms a film in a region other than the vicinity of the nozzle on the outer surface of the bushing plate, and a film using any one or more of ceramic, glass ceramics, and glass material groups as the film Forming a coating process;
A method for producing a bushing for producing glass long fibers, comprising: a firing step of heating the formed film so as to have a dense structure.   A long glass fiber manufacturing apparatus, wherein the long glass fiber manufacturing bushing according to any one of claims 1 to 6 is used to spin the long glass fiber.   A long glass fiber for a composite material is produced using the glass long fiber manufacturing apparatus according to claim 8 while monitoring the outer surface of the bushing plate and the spinning state of the long glass fiber. Production method.   The method for producing a long glass fiber according to claim 9, wherein the long glass fiber for composite material is any one of FRP, FRTP, and GRC applications.   The method for producing a long glass fiber according to claim 9 or 10, wherein the spinning status is monitored by any one or more of taking a spinning image, measuring a spinning speed, and measuring a fiber diameter.

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