JP6708311B1 - Coating liquid containing reinforcing fiber tape and coating liquid containing reinforcing fiber tape package manufacturing method - Google Patents

Abstract

The present invention suppresses the generation of fluff, and is capable of continuous production without clogging of fluff. Further, the reinforcing fiber tape is efficiently impregnated with the coating liquid, and the production speed can be increased. An object of the present invention is to provide a method for producing a tape, and a coating liquid containing the coating liquid is applied to the reinforcing fiber tape by passing a reinforcing fiber tape having a tape width of 3 to 30 mm inside the coating portion in which the coating liquid is stored. A method for manufacturing a reinforced fiber tape, wherein the applying part includes a liquid pool part and a narrow part communicating with each other, and the liquid pool part is a part where a cross-sectional area continuously decreases along a running direction of the reinforced fiber tape. The narrowed portion has a slit-shaped cross section and a cross-sectional area smaller than the upper surface of the liquid pool portion, and the width variation coefficient (CV) of the coating liquid-containing reinforced fiber tape pulled out from the narrowed portion is The purpose of the method is to produce a coating liquid-containing reinforcing fiber tape having a content of 5% or less.

Description

The present invention relates to a method for manufacturing a coating liquid-containing reinforcing fiber tape and a coating liquid-containing reinforcing fiber tape package, and more particularly to an efficient method for manufacturing a coating liquid-containing reinforcing fiber tape.

Fiber reinforced composite materials (FRP) made by reinforcing matrix resins including thermoplastic resins and thermosetting resins with reinforcing fibers are used for aviation/space materials, automobile materials, industrial materials, pressure vessels, building materials, housings, medical equipment. It is used in various fields such as applications and sports applications. Carbon fiber reinforced composite materials (CFRP) are widely and preferably used when particularly high mechanical properties and light weight are required. On the other hand, glass fiber reinforced composite material (GFRP) may be used when cost is prioritized over mechanical properties and lightness. In FRP, a reinforcing fiber bundle is impregnated with a matrix resin to obtain an intermediate base material, which is laminated and molded, and when a thermosetting resin is used, it is thermoset to produce a member made of FRP. In the above-mentioned applications, there are many flat objects and bent ones, and a two-dimensional sheet material is more suitable as an intermediate base material for FRP than a one-dimensional strand or roving material when producing a member. Widely used from the viewpoint of stacking efficiency and moldability.

Further, recently, in order to improve the production efficiency of members made of FRP, mechanization and automation of stacking of sheet-shaped intermediate base materials have been promoted, and narrow tape-shaped intermediate base materials are preferably used here. The narrow tape-shaped intermediate base material can be obtained by slicing a wide-width sheet-shaped intermediate base material into a desired width or by impregnating a narrow width reinforcing fiber sheet directly with a matrix resin.

A method for producing a carbon fiber UD base material will be briefly described. First, after firing a plurality of raw yarns, a surface treatment and a sizing agent are applied, and the yarns are wound on a bobbin as a carbon fiber tape. After that, the hot-melt method, which is one of the manufacturing methods of the prepreg, melts the matrix resin and then coats it on the release paper, and after producing a laminated structure sandwiching this on the upper surface and the lower surface of the reinforcing fiber sheet, heat and The matrix resin is impregnated into the reinforcing fiber sheet by pressure. This method has a problem that the number of steps is large, the production speed cannot be increased, and the cost is high.

Therefore, in the manufacturing process of carbon fibers, a method of manufacturing a prepreg in which carbon fibers immediately after the firing process are impregnated with a matrix resin has been proposed (Patent Document 1). By using this method, it is possible to simplify the steps of applying the sizing agent, winding the bobbin, and unwinding the carbon fiber at the time of producing the prepreg, and reduce the number of steps.

On the other hand, Patent Documents 2 to 6 described below also show how to improve the efficiency of coating and impregnating processes related to the prepreg manufacturing process.

As a method for increasing the efficiency of impregnation, there has been a proposal as disclosed in Patent Document 2, for example. This is a method in which glass fibers are melt-spun and bundled into strands or rovings which are passed through a liquid pool having a conical flow path filled with a thermoplastic resin.

On the other hand, a method of simultaneously forming a coating film on both sides of a sheet-like material is described in Patent Document 3, but this is to pass the sheet-like material through a web guide in order to prevent fluctuations of the sheet-like material at the time of forming the coating film. After that, it is applied with a pipe doctor.

As a method for manufacturing strip-shaped prepregs using a thermoplastic resin, a horizontal drawing method in which the strip-shaped reinforcing fiber bundle is conveyed in the horizontal direction (transverse direction) and passed through a die to apply and impregnate the strip-shaped reinforcing fiber bundle with the thermoplastic resin ( Patent document 4) is known. In Patent Document 3, a plurality of strip-shaped reinforcing fiber bundles are separately introduced into a die filled with a molten thermoplastic resin, and a fixed guide (for example, a squeeze bar) is used to open, impregnate, and stack the fibers, and finally 1 It is described that the sheet-shaped prepreg is pulled out from the die.

Patent Document 5 describes an apparatus that applies ultrasonic vibration to an outlet in a pull-through method in which a manifold is filled with a thermoplastic resin and a reinforcing fiber bundle is vertically pulled out.

In addition, as a method of producing a tow prepreg in which a matrix resin is applied to one yarn of a reinforcing fiber bundle among the prepregs, the matrix resin is applied by contacting the reinforcing fiber bundle with a kiss roll as described in Patent Document 6. Has been done.

It has been proposed to improve the coating method not only in the prepreg manufacturing process but also in the carbon fiber manufacturing process. For example, in Patent Document 7, a sizing agent is applied by roll coating and air is applied to the carbon fibers after application to adjust the application amount.

JP, 2003-268137, A International publication WO2001/028951 pamphlet JP, 10-337516, A International publication WO2012/002417 pamphlet Japanese Unexamined Patent Publication No. 1-178412 JP2012-184279A JP, 2003-278032, A

However, in the method of Patent Document 1, the end of the carbon fiber tape is not gripped when transferring the resin from the release paper to the carbon fiber tape or when applying the resin to the carbon fiber tape from the resin supply unit. In addition, the width of the tape and the basis weight of the resin may change.

The method of Patent Document 2 can only produce a strand or a roving-like material, and cannot be applied to the production of a sheet-like prepreg which is an object of the present invention. Further, in Patent Document 1, in order to improve the impregnation efficiency, a fluid of a thermoplastic resin is applied to the side surface of a strand or a roving-shaped reinforcing fiber bundle to actively generate turbulent flow in a conical flow path. It is considered that this is intended to cause the matrix resin to flow in by partially disturbing the arrangement of the reinforcing fiber bundle, but when this idea is applied to the reinforcing fiber sheet, the reinforcing fiber sheet is deformed and the quality of the prepreg is improved. It is considered that the mechanical properties of FRP are not only deteriorated but also deteriorated.

Further, when the technique of Patent Document 3 is applied, it is considered that fluff is generated by rubbing with the web guide, and the reinforcing fiber sheet becomes difficult to run. Further, the technique of Patent Document 2 is a resin coating, and impregnation is not intended.

Further, in the method of Patent Document 4, the fluff is likely to stay in the liquid pool portion during continuous production, and the fluff is likely to be clogged at the pull-out portion. In particular, when the band-shaped reinforcing fiber bundle is continuously run at a high speed, the frequency of clogging of fluff is extremely increased, so that the production can be performed only at a very low speed, and there is a problem that the productivity is not increased. Further, in the case of the horizontal drawing method, the die part needs to be sealed to prevent liquid leakage, and it is not sufficient to collect fluff during continuous production. Further, in the horizontal drawing method, when the matrix resin is impregnated inside the reinforcing fiber sheet, the bubbles remaining inside the band-shaped reinforcing fiber bundle are buoyant in the direction orthogonal to the orientation direction of the reinforcing fiber bundle (belt-like reinforcing). Since it is discharged in the thickness direction of the fiber bundle), bubbles are discharged by pushing away the impregnated matrix resin. Therefore, since the movement of bubbles is hindered by the liquid and the impregnation of the matrix resin is also hindered by the bubbles, there is a problem that the impregnation efficiency is poor. Further, it has been proposed to exhaust bubbles from the vent, but it is considered to be limited in the effect only in the vicinity of the die exit.

Further, in the method described in Patent Document 5, a nozzle portion which is not filled with resin is provided on the upper part of the manifold, and the nozzle can be optimized with a strand or roving-like material, but a flat surface such as a reinforcing fiber sheet. It is difficult to adapt to the shape, and it is considered that when the reinforcing fiber sheet passes through this, fluffs are generated, and when the fluff is brought into the manifold, it easily clogs with the die.

Further, the method using the kiss roll described in Patent Document 6 does not cause a problem when the production speed as described in the document is slow, but the production speed is further increased, and when the matrix resin has a low viscosity, resin scattering occurs. There is a possibility that there is a problem in that the surroundings of the apparatus become dirty and the process stability is lowered, or the production efficiency is lowered due to the stoppage of the apparatus for cleaning. Furthermore, the width fluctuation of the reinforcing fiber bundle on the kiss roll is essentially large, and this becomes remarkable especially when the production speed is increased, and the fluctuation of the applied amount of the matrix resin and the tow prepreg width may be large. Conceivable.

Further, in the coating method described in Patent Document 7, when the coating amount is adjusted by air, the process is contaminated by the scattering of the coating liquid to the surroundings, and the production efficiency is reduced due to the stoppage of the device for cleaning. Problems can occur. If applied to the application of the matrix resin, the amount of the matrix resin applied and the variation in the tow prepreg width may increase.

As described above, an efficient method for producing a coating liquid-containing reinforcing fiber tape using a narrow reinforcing fiber tape has not yet been established, and a coating liquid application method capable of improving tape width accuracy has not been established. It was

The subject of the present invention relates to a method for producing a coating liquid-containing reinforcing fiber tape, which suppresses the generation of fluff, and enables continuous production without clogging of the fluff, and further impregnates the reinforcing fiber tape with the coating liquid efficiently to produce. An object of the present invention is to provide a method for producing a coating liquid-containing reinforcing fiber tape, which can increase the speed.

In the method for producing a coating liquid-containing reinforcing fiber tape according to the present invention, which solves the above-described problems, a reinforcing fiber tape having a tape width of 3 to 30 mm is passed inside a coating portion in which the coating liquid is stored to strengthen the coating liquid. A method for producing a coating liquid-containing reinforced fiber tape applied to a fiber tape, wherein the coating part includes a liquid pool part and a narrowed part which are communicated with each other, and the liquid pool part is cut along a running direction of the reinforced fiber tape. The narrowed portion has a continuously decreasing area, the narrowed portion has a slit-shaped cross section, and has a cross-sectional area smaller than the upper surface of the liquid pool portion, and is regulated by a side plate member forming the liquid pool portion. The width L (mm) of the lower part of the liquid pool portion of the reinforcing fiber tape in the tape width direction and the width W (mm) of the tape-shaped reinforcing fiber immediately below the narrowed portion satisfy L≦1.1×W, A method for producing a coating liquid-containing reinforcing fiber tape in which the width variation coefficient (CV) of the coating liquid containing reinforcing fiber tape pulled out from the part is 5% or less.
Further, the method for producing a coating liquid-containing reinforcing fiber tape of the present invention is to pass the coating liquid to the reinforcing fiber tape by passing a reinforcing fiber tape having a tape width of 3 to 30 mm inside the coating portion in which the coating liquid is stored. A method for producing a coating liquid-containing reinforced fiber tape obtained by applying, wherein the coating part comprises a liquid pool part and a narrow part communicating with each other, and the liquid pool part is cut along a running direction of the reinforcing fiber tape. The constriction has a slit-shaped cross section and has a cross-sectional area smaller than the upper surface of the liquid pool, and restricts the width of the reinforcing fiber tape in the liquid pool. A width regulating mechanism that is a plate-shaped bush along the inner shape of the coating portion from the middle portion to the lower portion for width regulation of the width W (mm) of the reinforcing fiber tape immediately below the narrowed portion and the width regulating mechanism lower end. The relationship with the width L2 (mm) regulated by the mechanism satisfies L2≦1.1×W (mm), and the width variation coefficient (CV) of the coating liquid containing reinforced fiber tape pulled out from the narrowed portion is 5%. The following is a method for producing a coating liquid containing reinforcing fiber tape.

Further, the method for producing a coating liquid-containing reinforcing fiber tape package of the present invention is a method for producing a coating liquid containing reinforcing fiber tape package in which the coating liquid containing reinforcing fiber tape is traversed or wound into a disc shape.

According to the method for producing a coating liquid-containing reinforcing fiber tape of the present invention, clogging due to fluff can be significantly suppressed and prevented. Further, since the coating liquid-containing reinforcing fiber tape can be obtained with high width accuracy, it is expected that the degree of freedom in design and the processing accuracy in applications such as application to prepregs can be improved. Further, the reinforcing fiber tape can be continuously run, the productivity is improved, and a high-quality coating liquid-containing reinforcing fiber tape without breakage can be obtained.

FIG. 1 is a schematic cross-sectional view showing a coating liquid-containing reinforcing fiber tape manufacturing method and a coating apparatus according to an embodiment of the present invention. FIG. 1 is a schematic cross-sectional view showing a coating liquid-containing reinforcing fiber tape manufacturing method and a coating apparatus according to an embodiment of the present invention. FIG. 1 is a schematic cross-sectional view showing a coating liquid-containing reinforcing fiber tape manufacturing method and a coating apparatus according to an embodiment of the present invention. FIG. 1 is a schematic cross-sectional view showing a coating liquid-containing reinforcing fiber tape manufacturing method and a coating apparatus according to an embodiment of the present invention. It is a detailed transverse cross-sectional view which expanded the part of the application part 20 in FIG. 1a. FIG. 3 is a schematic cross-sectional view showing a coating liquid-containing reinforcing fiber tape manufacturing method and a coating apparatus according to another embodiment of the present invention. FIG. 3 is a schematic cross-sectional view showing a coating liquid-containing reinforcing fiber tape manufacturing method and a coating apparatus according to another embodiment of the present invention. FIG. 3 is a schematic cross-sectional view showing a coating liquid-containing reinforcing fiber tape manufacturing method and a coating apparatus according to another embodiment of the present invention. FIG. 3 is a schematic cross-sectional view showing a coating liquid-containing reinforcing fiber tape manufacturing method and a coating apparatus according to another embodiment of the present invention. FIG. 3 is a bottom view of the coating unit 20 in FIG. 2 viewed from the direction of A in FIG. 2. It is sectional drawing explaining the structure inside an application part when the application part 20 in FIG. 2 is seen from the direction of B of FIG. It is sectional drawing showing the flow of the coating liquid 2 in the clearance gap 26 in FIG. 4a. It is a figure which shows the installation example of a width control mechanism. FIG. 3 is a schematic cross-sectional view showing a coating liquid-containing reinforcing fiber tape manufacturing method and a coating device according to an embodiment of the present invention, which is equipped with a cooling device 61. FIG. 4 is a detailed cross-sectional view of a coating unit 20b of another embodiment different from FIG. FIG. 7 is a detailed cross-sectional view of a coating unit 20c of another embodiment different from FIG. FIG. 7 is a detailed transverse cross-sectional view of a coating unit 20d of another embodiment different from FIG. FIG. 7 is a detailed cross-sectional view of a coating unit 20e of another embodiment different from FIG. It is a detailed cross-sectional view of the application part 30 of embodiment different from this invention. It is a figure which shows the aspect provided with the bar in the liquid reservoir which is an example of embodiment of this invention. It is the schematic which shows the example of the prepreg tape manufacturing process and apparatus which used this invention. It is the schematic which shows the example of the manufacturing process and apparatus of the coating liquid containing reinforced fiber tape using this invention. It is the schematic which shows the example of the manufacturing process and apparatus of the coating liquid containing reinforced fiber tape using this invention. It is the schematic which shows the example of the manufacturing process and apparatus of the coating liquid containing reinforced fiber tape using this invention. It is a schematic diagram of an example of another prepreg tape manufacturing process and device using the present invention. FIG. 3 is a schematic view of an example of another coating liquid-containing reinforcing fiber tape manufacturing process/apparatus using the present invention. It is a figure which shows the example of the aspect of multi-line-ization based on one Embodiment of this invention. It is a figure which shows the example of the aspect of multi-line-ization based on one Embodiment of this invention. It is a figure which shows the example of the aspect of multi-line-ization based on one Embodiment of this invention. It is a figure which shows the example of the aspect of multi-line-ization based on one Embodiment of this invention. It is a figure showing an example of a mode which laminates a plurality of prepreg tapes concerning one embodiment of the present invention. It is a figure which shows the example of the aspect provided with the some application part which concerns on one Embodiment of this invention. It is a schematic diagram of an example of another prepreg tape manufacturing process and device using the present invention. It is a schematic diagram of an example of another prepreg tape manufacturing process and device using the present invention. It is a schematic diagram of an example of another prepreg tape manufacturing process and device using the present invention. FIG. 3 is a schematic view of an example of another coating liquid-containing reinforcing fiber tape manufacturing process/apparatus using the present invention. FIG. 3 is a schematic view of an example of another coating liquid-containing reinforcing fiber tape manufacturing process/apparatus using the present invention. FIG. 3 is a schematic view of an example of another coating liquid-containing reinforcing fiber tape manufacturing process/apparatus using the present invention. FIG. 3 is a schematic view of an example of another coating liquid-containing reinforcing fiber tape manufacturing process/apparatus using the present invention. FIG. 3 is a schematic view of an example of another coating liquid-containing reinforcing fiber tape manufacturing process/apparatus using the present invention.

Preferred embodiments of the present invention will be described with reference to the drawings. It should be noted that the following description exemplifies embodiments of the present invention, and the present invention is not construed as being limited thereto, and various modifications can be made without departing from the objects and effects of the present invention. ..

<Outline of method for producing coating liquid-containing reinforcing fiber tape>
First, the outline of the method for producing the coating liquid-containing reinforcing fiber tape of the present invention will be described with reference to FIGS. FIG. 1a is a schematic cross-sectional view showing a method and an apparatus for producing a coating liquid-containing reinforcing fiber tape according to an embodiment of the present invention. The coating device 100 is provided between the transport rolls 13 and 14 which are a traveling mechanism that causes the reinforcing fiber tape 1a to travel substantially vertically downward Z, and the coating liquid 2 is stored therein. A coating unit 20 is provided. In addition, before and after the coating device 100, a creel 11 for unwinding the reinforcing fibers 1 and a reinforcing fiber tape 1a (in FIG. 1, arranged in the depth direction of the paper surface) in which the unwound reinforcing fibers 1 are arranged in one direction are obtained. The arranging device 12 and the coating liquid-containing reinforcing fiber tape 1b winding device 15 can be provided, and the coating device 100 is provided with a coating liquid supply device (not shown). Further, a supply device 16 for supplying the release tape 3 is provided as needed. In the present invention, the coating liquid-containing reinforcing fiber tape means that the coating liquid is applied to the reinforcing fiber tape, the coating liquid may be present on the surface, a part of the coating liquid, or the entire coating liquid. May be impregnated inside the reinforcing fiber tape. Although FIG. 1a shows the mechanism in which the coating device travels vertically, it may travel horizontally as shown in FIG. 1b, as described later.

Further, FIG. 1c is a schematic view of a method for producing a coating liquid-containing reinforcing fiber tape having a firing step in a step before the coating apparatus 100 of FIG. 1a. In the production method of the present invention, a carbon fiber tape may be used as the reinforcing fiber tape, and the steps from the firing step 11 at which the highest temperature reaches 1000 to 3000° C. to the step of applying the coating liquid may be continuous. The term "continuous" as used herein means that the carbon fibers are fired and then arranged into a tape to form a reinforced fiber tape, and the carbon fiber is added until the coating liquid is applied to the reinforced fiber tape. It means that there is no cutting step. That is, the linear velocity at which the carbon fiber is produced, the linear velocity at which the coating liquid is applied in the coating portion, and the linear velocity at the time of winding the coating liquid-containing reinforcing fiber tape are basically the same. Here, before applying the coating liquid, a surface treatment step, a sizing step, a drying step, a carbon fiber tape smoothing device, and a widening device described later can be performed. The carbon fiber exits the firing step 11 and is guided to the coating apparatus 100. As in FIG. 1a, the coating device 100 is provided between the transport rolls 13 and 14 for guiding the reinforcing fiber tape 1a made of carbon fiber into the coating device 100 and the transport rolls 13 and 14, and The coating unit 20 in which 2 is stored is provided. Further, as in FIG. 1a, a winding device 15 can be provided after the coating device 100, and the coating device 100 is provided with a coating liquid supply device (not shown). Further, if necessary, as in the case of FIG. 1A, a supply device 16 for supplying the release tape 3 is provided. Further, FIG. 1c shows the mechanism in which the coating device is running in the vertical direction, but as described later, the reinforcing fiber tape may be run in the horizontal direction as shown in FIG. 1d. When preparing the fired carbon fibers into a tape shape, it is possible to obtain them without using a special device if the running paths of the carbon fibers are arranged in an orderly manner at the exit of the firing process. 1d does not show a device for arranging the fired carbon fibers into a tape. Of course, in order to arrange the carbon fibers into a tape shape, a mechanism such as a guide or a roll that arranges the fibers may be used.

<Reinforcing fiber tape>
Here, examples of the reinforcing fiber 1 include carbon fiber, glass fiber, metal fiber, metal oxide fiber, metal nitride fiber, organic fiber (aramid fiber, polybenzoxazole fiber, polyvinyl alcohol fiber, polyethylene fiber, etc.). However, it is preferable to use carbon fiber from the viewpoint of mechanical properties and lightness of FRP.

As the reinforcing fiber tape, a unidirectional material (UD base material) in which a plurality of reinforcing fibers are arranged in one direction on a surface, or a reinforcing fiber in which reinforcing fibers are arranged in multiple axes or are randomly arranged to form a tape There is a fabric.

A known method can be used as a method for forming the UD substrate, and there is no particular limitation, but a reinforcing fiber bundle in which single fibers are arranged in advance is formed, and the reinforcing fiber bundle is further arranged to form a reinforcing fiber tape. The formation is preferable from the viewpoint of process efficiency and uniform arrangement. For example, in carbon fiber, a tow, which is a tape-shaped reinforcing fiber bundle, is wound around a bobbin. The tape-shaped reinforcing fiber bundle extracted from this is used in one yarn, or these are arranged in a plurality of yarns. Then, a reinforcing fiber tape can be obtained. Further, it has a reinforcing fiber arrangement mechanism for arranging the reinforcing fiber bundles drawn out from the bobbin wound on the creel in an orderly manner and eliminating the undesired overlapping and folding of the reinforcing fiber bundles in the reinforcing fiber tape and the gaps between the reinforcing fiber bundles. Preferably. As the reinforcing fiber arrangement mechanism, a known roller, comb-type arrangement device, or the like can be used. Further, stacking a plurality of reinforcing fiber tapes arranged in advance is also useful from the viewpoint of reducing the gap between the reinforcing fibers. The creel is preferably provided with a tension control mechanism when pulling out the reinforcing fiber. As the tension control mechanism, a known mechanism can be used, and a brake mechanism or the like can be used. Further, the tension can be controlled by adjusting the yarn path guide or the like. In the present invention, the reinforcing fiber bundles can be arranged so as to have a desired width of the reinforcing fiber tape.

On the other hand, specific examples of the reinforced fiber fabric include woven fabrics and knitted fabrics, two-dimensionally reinforced fiber reinforced fibers, and non-woven fabrics, mats, and papers in which reinforced fibers are randomly oriented. .. In this case, the reinforcing fibers can be formed into a tape by using a method such as applying a binder, entanglement, welding or fusing. As the woven fabric, non-crimp woven fabrics, bias structures, entangled woven fabrics, multiaxial woven fabrics, multiple woven fabrics and the like can be used in addition to plain weave, twill and satin basic weave designs. The woven fabric in which the bias structure and the UD substrate are combined is not only the UD structure that suppresses the deformation of the woven fabric due to the tension in the coating/impregnation process but also the pseudo isotropic property of the bias structure, which is a preferable form. .. In addition, the multiple woven fabric has the advantage that the upper and lower faces of the woven fabric and the structure and characteristics inside the woven fabric can be designed. For knitting, warp knitting is preferable in consideration of shape stability in the coating/impregnation process, but a braid which is a tubular knitting can also be used. When the reinforcing fiber fabric is formed into a tape, the reinforcing fiber fabric may be prepared so as to have a desired width from the beginning, or the reinforcing fiber fabric may be formed and then cut to have a desired width. ..

Of these, when giving priority to the mechanical properties of FRP, it is preferable to use a UD base material, and the UD base material can be produced by a known method of arranging reinforcing fibers in a tape shape in one direction. ..

<How to use the coating liquid-containing reinforcing fiber tape>
In recent years, in order to make the prepreg laminating process more efficient, a device called AFP (Automated Fiber Placement) for automatically laminating prepreg tape has been widely used in aircraft applications, etc. Therefore, it is important that the tape width is 3 to 30 mm (3 mm or more and 30 mm or less). In addition, for pressure vessels and the like, a manufacturing method called filament winding has been conventionally used. At this time, a matrix resin is applied to one yarn (tow) of a reinforcing fiber bundle in a resin tank, and the pressure vessel liner is used as it is. This is wrapped around. When used for this purpose, the width of the reinforced fiber tape is about the same as the tow of one yarn (usually about 6 to 12 mm), but in some cases, the width of even one yarn can be increased by performing widening processing. It is also possible to widen it to 30 mm. A wide reinforced fiber tape is preferable because when the coating liquid-containing reinforced fiber tape is laminated, a gap between the tapes, that is, a portion without a reinforced fiber is less likely to occur.

<Carbon fiber tape>
The carbon fiber tape in the present invention is a tape-shaped carbon fiber which is a reinforcing fiber, and may be formed from one carbon fiber yarn bundle or may be formed from a plurality of carbon fiber yarns.

As carbon fibers, so-called carbonized yarns, graphite yarns obtained by a known method using various fibers such as acrylic fibers, pitch fibers, and cellulose fibers as precursors, those surface-oxidized, and sizing treatments thereof The ones that have been included are included.

Among carbon fibers, a method for producing a polyacrylonitrile-based carbon fiber will be described as an example. As a spinning method for obtaining the precursor fiber of the carbon fiber, a spinning method such as a wet type, a dry type and a dry type can be used.

In the wet spinning method, a solution obtained by dissolving a homopolymer or copolymer of polyacrylonitrile in a solvent can be used as the spinning dope. As the solvent, an organic solvent such as dimethyl sulfoxide, dimethylformamide or dimethylacetamide, or an aqueous solution of an inorganic compound such as nitric acid, sodium rhodanate, zinc chloride or sodium thiocyanate is used.

The above spinning solution is spun through a spinneret and discharged into a spinning bath to coagulate. As the spinning bath, an aqueous solution of the solvent used as the solvent of the spinning dope can be used. The fiber coagulated in the spinning bath is washed with water and drawn to obtain a precursor fiber. The precursor fiber thus obtained is subjected to a flameproofing treatment and a carbonization treatment as a firing step, and if necessary, a graphitization treatment to obtain a carbon fiber. The heating temperature in the firing step is 1000 to 3000° C., which is the highest temperature.

The carbon fiber tape is obtained by shaping the precursor fiber into a flat cross-sectional shape, for example, an elliptical shape, and firing it, or shaping the obtained carbon fiber yarn bundle into a flat cross-sectional shape. Or by arranging a plurality of carbon fiber yarns to obtain a tape-like shape.

<Surface treatment of carbon fiber tape>
The carbon fiber tape is subjected to an oxidation treatment, if necessary, in order to improve the adhesiveness with the matrix resin for each carbon fiber single yarn, and an oxygen-containing functional group is introduced on the surface. As the oxidation treatment method, gas phase oxidation, liquid phase oxidation, and liquid phase electrolytic oxidation are used. From the viewpoint of high productivity and uniform treatment, liquid phase electrolytic oxidation is generally used.

Examples of the electrolytic solution used in the liquid-phase electrolytic oxidation include an acidic electrolytic solution and an alkaline electrolytic solution. Examples of the acidic electrolytic solution include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, boric acid, and carbonic acid; organic acids such as acetic acid, butyric acid, oxalic acid, acrylic acid, and maleic acid; or ammonium sulfate or ammonium hydrogen sulfate. And the like. Specific examples of the alkaline electrolyte include aqueous solutions of hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide; sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, Aqueous solution of carbonate such as barium carbonate and ammonium carbonate; Aqueous solution of hydrogen carbonate such as sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate, barium hydrogen carbonate and ammonium hydrogen carbonate; ammonia, tetraalkylammonium hydroxide And an aqueous solution of hydrazine and the like.

From the viewpoint that the formation of covalent bonds between the matrix resin and the oxygen-containing functional groups on the carbon fiber surface is promoted, and the adhesiveness is further improved, after the carbon fiber tape is subjected to electrolytic oxidation treatment with an alkaline electrolyte, or the carbon fiber tape is acidified. The matrix resin may be applied after electrolytically oxidizing treatment in an aqueous solution and subsequently washing with an alkaline aqueous solution.

Specific examples of the alkaline aqueous solution used for washing include aqueous solutions of hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide; sodium carbonate, potassium carbonate, magnesium carbonate, carbonic acid. Aqueous solution of carbonate such as calcium, barium carbonate and ammonium carbonate; Aqueous solution of hydrogen carbonate such as sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate, barium hydrogen carbonate and ammonium hydrogen carbonate; ammonia, tetra hydroxide Examples thereof include aqueous solutions of alkylammonium and hydrazine. As a method of washing the carbon fiber tape with an alkaline aqueous solution, for example, a dipping method and a spray method can be used.

The carbon fiber tape may be washed with water and dried after being subjected to liquid phase electrolytic oxidation treatment or an alkaline aqueous solution.

<Sizing process>
The carbon fiber tape may be subjected to a sizing treatment in order to impart sizing property to the obtained carbon fiber tape. The method for applying the sizing agent is not particularly limited, but it is preferable to use the coating apparatus 100 described later, because the coating amount can be accurately applied and the sizing agent can be applied to the inside of the tape on the carbon fiber tape. When using the coating apparatus 100, the carbon fiber tape may be run vertically as shown in FIG. 1a, or may be run horizontally as shown in FIG. 1b.

The sizing agent is used as an aqueous solution or an aqueous dispersion, or an organic solvent solution, which imparts a focusing property to the carbon fiber tape, improves bending resistance and abrasion resistance, and combines the carbon fiber tape with the composite material. Any sizing agent that provides good composite material properties when used as a reinforcing fiber in the material may be used.

To the sizing agent used as an aqueous solution and/or an aqueous dispersion, for example, a polyalkylene oxide and its derivative, polyvinylpyrrolidone and its derivative, a water-soluble resin such as polyvinyl alcohol, or various surfactants may be added to disperse the water. Various known resins such as an epoxy resin and an unsaturated polyester resin to be used can be mentioned.

Further, the sizing agent used as an organic solvent solution, for example, glycidyl ether type, glycidyl ester type, glycidyl amine type, aliphatic epoxide type epoxy resin, unsaturated polyester resin, polyamide resin, known various resins such as polyimide resin Is mentioned.

Any organic solvent may be used as long as it can stably dissolve the resin, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone and methyl ethyl ketone, carbon tetrachloride, trichlene and chloroform. Examples thereof include halogenated hydrocarbons and modified ethers such as cellosolve, but are not particularly limited to the above resins. It may be appropriately selected depending on the boiling point and industrial handling. The organic solvent-based sizing agent may be used as a mixture of two or more kinds.

Specifically, sizing comprising (A) an epoxy resin, (B) a condensate of an unsaturated dibasic acid and an alkylene oxide adduct of a bisphenol, and (C) an alkylene oxide adduct of a phenol. Examples thereof include glycidyl type epoxy resins and non-glycidyl type (peracetic acid type) epoxy resins. The glycidyl type epoxy resin is a bisphenol type, for example, obtained by condensation of epichlorohydrin and bisphenols such as bisphenol A, bisphenol F, 2,2'-bis(4-hydroxyphenyl)butane. There is a phenol type, for example, a novolac type phenol resin reacted with epichlorohydrin, and an ester type, for example, a glycidyl methacrylate ester and an ethylenic double bond-containing unit amount. Examples thereof include copolymers with the body (for example, acrylonitrile, styrene, vinyl acetate, vinyl chloride). Examples of the non-glycidyl epoxy resin include cyclic resin group epoxy resins, epoxidized butadiene, epoxidized glyceride, and epoxidized soybean oil.

Examples of the unsaturated dibasic acid in the condensate of (B) include fumaric acid, maleic acid, citraconic acid, and itaconic acid, and examples of the alkylene oxide adduct of bisphenols include the bisphenols described in the section (A). -Alkylene oxide (ethylene oxide (EC), propylene oxide (PO), butylene oxide (BO), etc.) adduct (in the case of two or more alkylene oxide adducts, a random or block adduct).

As the component (C), monocyclic phenol (phenol having one aromatic ring), for example, phenol, phenol having one or more alkyl groups, polyvalent phenol and polycyclic phenol (Phenol having two or more aromatic rings) such as phenylphenol, cumylphenol, benzylphenol, hydroquinonemonophenylether, naphthol, bisphenol, monocyclic phenol and the like. Alkylene oxide (eg, EO, PO, BO) adduct of phenols selected from reaction products (referred to as styrenated phenols) with styrenes (styrene, α-methylstyrene, etc.) (two or more kinds) In the case of an alkylene oxide adduct, a block or random adduct is mentioned.

The aqueous solution, aqueous dispersion or organic solvent solution of the sizing agent may be prepared by a conventionally known method depending on the characteristics of the sizing agent. The carbon fiber tape can be obtained by applying a sizing agent-containing liquid to heat treatment, removing the solvent contained in the sizing agent-containing liquid, and drying.

Thus, the manufacturing method of the present invention can be used as a method for applying a sizing agent to a carbon fiber tape. It can also be used as a method for coating a resin on a carbon fiber tape to which a sizing agent has been applied, as described later.

<Control of reinforcing fiber tension>
In the production method of the present invention, the reinforcing fibers hung on the creel are uniformly drawn, and in order to improve the width accuracy of the reinforcing fiber tape, and thus the coating liquid-containing reinforcing fiber tape, the tension at the time of drawing the reinforcing fibers from the creel is adjusted. It is preferable to control. For this purpose, the yarns are aligned and nipped, and a method of controlling the tension by giving a speed difference to the equipment of the subsequent process by a driving device and a direction change guide roll as described in JP-A-2005-248360. Examples thereof include a driving method and a method using a roll to which a powder brake is connected as described in JP-A-2004-162055. It is also possible to use a creel having a brake mechanism on the spindle portion on which the reinforcing fiber bobbin is mounted. The brake mechanism includes a band brake and an electromagnetic type. As the electromagnetic method, there is a method of providing a magnetic force type torque control equipment using a permanent magnet on the spindle shaft. As the electromagnetic brake mechanism, for example, one described in JP 2012-184076 A can be exemplified. Furthermore, tension control can be performed via a dancer roll. Among these, it is preferable to use a creel equipped with an electromagnetic brake mechanism from the viewpoint of precision of tension control and downsizing of a manufacturing apparatus.

<Smoothing of reinforcing fiber tape>
In the present invention, by increasing the smoothness of the surface of the reinforcing fiber tape, it is possible to improve the uniformity of the coating amount in the coating portion. For this reason, it is preferable to guide the reinforcing fiber tape to the liquid pool after smoothing it. The smoothing method is not particularly limited, and examples thereof include a method of physically pressing with a facing roll or the like, a method of moving the reinforcing fiber using an air flow, and the like. The physical pressing method is preferable because it is simple and does not easily disturb the arrangement of the reinforcing fibers. More specifically, calendar processing or the like can be used. The method using an air flow is preferable because not only scratching does not easily occur but also the reinforcing fiber tape is widened.

<Width expansion of reinforcing fiber tape>
Further, in the present invention, it is also preferable that the reinforcing fiber tape is subjected to a widening treatment and then guided to the coating portion from the viewpoint of efficiently producing a wide coating liquid-containing reinforcing fiber tape. When the tape width is wide, it is considered that the cover area when the prepreg tapes are laminated becomes large and there is an advantage that the gap during lamination can be suppressed. The widening method is not particularly limited, but examples thereof include a method of mechanically applying vibration and a method of expanding the reinforcing fiber bundle by an air flow. As a method of mechanically applying vibration, for example, as described in JP-A-2015-22799, there is a method of bringing a reinforcing fiber sheet into contact with a vibrating roll. As the vibration direction, when the traveling direction of the reinforcing fiber tape is the X axis, it is preferable to give vibrations in the Y axis direction (horizontal direction) and the Z axis direction (vertical direction). It is also preferable to use them in combination. In addition, it is preferable to provide a plurality of protrusions on the surface of the vibrating roll, because the rubbing of the reinforcing fibers on the roll can be suppressed. As a method using an air flow, for example, SEN-I GAKKAISHI, vol. 64, P-262-267 (2008). The described method can be used.

<Preheating of reinforcing fiber tape>
Further, in the present invention, when the coating liquid temperature is set higher than room temperature, when the reinforcing fiber tape is heated and then led to the liquid pool portion, the temperature decrease of the tape is suppressed and the viscosity uniformity of the coating liquid is improved. It is preferable because it can be caused. The reinforcing fiber tape is preferably heated to a temperature near the coating liquid temperature, but heating means for this purpose include air heating, infrared heating, far infrared heating, laser heating, contact heating, heating medium heating (steam, etc.), etc. Any means can be used. Among them, infrared heating is preferable because the device is simple and the reinforcing fiber tape can be directly heated, so that heating to a desired temperature can be efficiently performed even when the traveling speed is high.

<Coating liquid>
The coating liquid used in the present invention can be appropriately selected according to the purpose of application. Examples of the coating liquid include liquids containing a sizing agent, a surface modifier, and other agents that impart sizing and functionality as described above, as well as a matrix resin for forming a prepreg tape.

The matrix resin used in the present invention can be used as a resin composition containing various resins and particles described below, a curing agent, and various additives. When the present invention is applied to the production of a prepreg tape, the reinforcing fiber tape is impregnated with a matrix resin as a coating liquid, and the prepreg tape can be laminated and molded as it is to obtain a member made of FRP. The degree of impregnation can be controlled by the design of the coating section and additional impregnation after coating. The matrix resin can be appropriately selected according to the application, but a thermoplastic resin or a thermosetting resin is generally used. The matrix resin may be a molten resin that is heated and melted or a matrix resin that is melted at room temperature. Further, it may be a solution or varnished using a solvent. When the present invention is used for producing a prepreg tape, the coating liquid-containing reinforcing fiber tape may be referred to as a prepreg tape.

As the matrix resin, those generally used for FRP such as thermoplastic resin, thermosetting resin, and photocurable resin can be used. Further, if these are liquids at room temperature, they may be used as they are, and if they are solids or viscous liquids at room temperature, they may be heated to reduce their viscosity, or they may be melted and used as a melt, or a solvent. It may be dissolved in to form a solution or varnish.

The thermoplastic resin has a main chain selected from carbon/carbon bond, amide bond, imide bond, ester bond, ether bond, carbonate bond, urethane bond, urea bond, thioether bond, sulfone bond, imidazole bond and carbonyl bond. A polymer having a bond can be used. Specifically, polyacrylate, polyolefin, polyamide (PA), aramid, polyester, polycarbonate (PC), polyphenylene sulfide (PPS), polybenzimidazole (PBI), polyimide (PI), polyetherimide (PEI), polysulfone. (PSU), polyethersulfone (PES), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyaryletherketone (PAEK), polyamideimide (PAI), etc. it can. PPS, PES, PI, PEI, PSU, PEEK, PEKK, PAEK and the like are suitable in fields requiring heat resistance such as aircraft applications. On the other hand, in industrial applications, automobile applications, etc., polyolefins such as polypropylene (PP), PA, polyesters, PPS, etc. are suitable in order to improve the molding efficiency. These may be polymers, or oligomers or monomers may be used because of low viscosity and low temperature coating. Of course, these may be copolymerized depending on the purpose, or various kinds of them may be mixed and used as a polymer blend or a polymer alloy.

Examples of the thermosetting resin include an epoxy resin, a maleimide resin, a polyimide resin, a resin having an acetylene end, a resin having a vinyl end, a resin having an allyl end, a resin having a nadic acid end, and a resin having a cyanate end. Be done. These can generally be used in combination with a curing agent or a curing catalyst. Further, it is also possible to appropriately mix and use these thermosetting resins.

As the thermosetting resin suitable for the present invention, an epoxy resin is preferably used because it has excellent heat resistance, chemical resistance, and mechanical properties. In particular, an epoxy resin having an amine, a phenol, or a compound having a carbon-carbon double bond as a precursor is preferable. Specifically, as an epoxy resin having amines as precursors, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, various isomers of triglycidylaminocresol, and phenols are precursors. As the epoxy resin to be a body, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, and a compound having a carbon-carbon double bond as a precursor. Examples of the epoxy resin include, but are not limited to, alicyclic epoxy resin and the like. Brominated epoxy resins obtained by brominating these epoxy resins are also used. Epoxy resins having an aromatic amine represented by tetraglycidyldiaminodiphenylmethane as a precursor have good heat resistance and good adhesion to reinforcing fibers, and are most suitable for the present invention.

The thermosetting resin is preferably used in combination with a curing agent. For example, in the case of an epoxy resin, the curing agent may be any compound having an active group capable of reacting with an epoxy group. A compound having an amino group, an acid anhydride group or an azido group is preferable. Specifically, dicyandiamide, various isomers of diaminodiphenyl sulfone, and aminobenzoic acid esters are suitable. More specifically, dicyandiamide is preferred because it has excellent storage stability for prepreg. Further, various isomers of diaminodiphenyl sulfone are most suitable for the present invention because they give a cured product having good heat resistance. As the aminobenzoic acid esters, trimethylene glycol di-p-aminobenzoate and neopentyl glycol di-p-aminobenzoate are preferably used. Compared to diaminodiphenyl sulfone, they are inferior in heat resistance, but have high tensile strength. Since it is excellent, it is selected and used according to the application. Also, of course, a curing catalyst can be used if necessary. Further, in order to improve the pot life of the matrix resin, it is possible to use a curing agent or a curing catalyst in combination with a complexing agent capable of forming a complex.

Further, in the present invention, it is also preferable to use a thermosetting resin mixed with a thermoplastic resin. The mixture of thermosetting resin and thermoplastic resin gives better results than using the thermosetting resin alone. This is because thermosetting resins can be low-pressure molded by an autoclave while generally having a brittle defect, while thermoplastic resins are generally tough, but low-pressure molding by an autoclave is difficult. This is because they have the trade-off property of being present, and the physical properties and moldability can be balanced by using them in combination. When mixed and used, the thermosetting resin is preferably contained in an amount of more than 50% by mass from the viewpoint of the mechanical properties of FRP obtained by curing the prepreg tape.

<Polymer particles>
Further, in the present invention, inorganic particles or organic particles can be contained in the coating liquid or the matrix resin. The inorganic particles are not particularly limited, but for example, carbon particles, boron nitride particles, titanium dioxide particles, silicon dioxide particles, and the like can be preferably used in order to impart conductivity, heat conductivity, thixotropy, and the like. The organic particles are also not particularly limited, but it is particularly preferable to use polymer particles because the toughness, impact resistance, vibration damping property and the like of the obtained FRP can be improved. At this time, it is preferable that the glass transition temperature (Tg) or melting point (Tm) of the polymer particles is higher than the matrix resin temperature by 20° C. or more because the shape of the polymer particles can be easily retained in the matrix resin. The Tg of the polymer particles can be measured under the following conditions using a temperature modulation DSC. As the temperature modulation DSC device, Q1000 manufactured by TA Instruments is suitable, and it can be used after being calibrated with high-purity indium under a nitrogen atmosphere. The measurement conditions can be a temperature rising rate of 2° C./min, a temperature modulation condition of a period of 60 seconds and an amplitude of 1° C. The reversible component can be separated from the total heat flow thus obtained, and the temperature at the midpoint of the stepwise signal can be taken as Tg.

Further, Tm can be measured by an ordinary DSC at a temperature rising rate of 10° C./min, and the peak top temperature of a peak-like signal corresponding to melting can be taken as Tm.

Further, the polymer particles are preferably insoluble in the matrix resin, and as such polymer particles, for example, referring to the description of WO2009/142231 pamphlet, etc., suitable particles can be used. More specifically, polyamides and polyimides can be preferably used, and polyamides are most preferable because they can greatly improve impact resistance due to their excellent toughness. As the polyamide, polyamide 12, polyamide 11, polyamide 6, polyamide 66 or polyamide 6/12 copolymer, a semi-IPN (polymer interpenetrating network structure) with the epoxy compound described in Example 1 of JP-A No. 01-104624 is used. A modified polyamide (semi-IPN polyamide) or the like can be preferably used. The shape of the thermoplastic resin particles may be spherical particles, non-spherical particles, or porous particles, but spherical particles are particularly preferable in the production method of the present invention because they do not deteriorate the resin flow characteristics. Further, the spherical shape is a preferable mode in that there is no starting point of stress concentration and high impact resistance is given.

Commercially available polyamide particles include SP-500, SP-10, TR-1, TR-2, 842P-48, 842P-80 (all manufactured by Toray Industries, Inc.), "Organsol (registered trademark)" 1002D. , 2001UD, 2001EXD, 2002D, 3202D, 3501D, 3502D (manufactured by Arkema Co., Ltd.), "Grillamide (registered trademark)" TR90 (manufactured by Mzaberke Co., Ltd.), "TROGAMID (registered trademark)" CX7323, CX9701. , CX9704, (manufactured by Degussa Co., Ltd.) and the like can be used. These polyamide particles may be used alone or in combination.

Further, when the demand for heat resistance of FRP is not strict, particles of polyurethane type, rubber type, core shell rubber type, etc. are used for the purpose of adjusting the rheological properties of the coating liquid and improving the toughness and vibration damping property of FRP. It is also possible.

In order to increase the toughness of the reinforced fiber interlayer resin layer of FRP, it is preferable to retain the polymer particles in the reinforced fiber interlayer resin layer. Therefore, the number average particle size of the polymer particles is preferably in the range of 5 to 50 μm, more preferably in the range of 7 to 40 μm, and further preferably in the range of 10 to 30 μm. By setting the number average particle size to 5 μm or more, the particles do not enter the bundle of reinforcing fibers and can stay in the reinforced fiber interlayer resin layer of the obtained fiber reinforced composite material. By setting the number average particle size to 50 μm or less, the thickness of the matrix resin layer on the surface of the prepreg tape can be optimized, and the fiber mass content can be optimized in the obtained FRP.

<Viscoelasticity of coating liquid>
The coating liquid used in the present invention preferably has an optimum viscosity selected from the viewpoint of process passability and stability. Specifically, when the viscosity is in the range of 0.01 to 60 Pa·s, it is possible to suppress the liquid dripping at the outlet of the narrowed portion and improve the high-speed running property and stable running property of the reinforcing fiber sheet, which is preferable. When the viscosity of the coating liquid is 2 Pa·s or less, stable traveling is possible even when the traveling speed of the reinforcing fiber tape is 100 m/min or more, and further scattering of the coating liquid can be suppressed, which is preferable. The coating liquid viscosity is preferably 0.9 Pa·s or less.

Here, the viscosity refers to the coating liquid viscosity at the coating liquid temperature measured in the liquid pool portion, and more specifically, using a viscoelasticity measuring device such as a parallel disk type or a cone type, strain It is the viscosity at the coating liquid temperature measured at the liquid pool portion, measured at a speed of 3.14 s ^-1 . The loss elastic modulus can be measured in the same manner as the above-described viscosity measurement, and is the loss elastic modulus at the coating liquid temperature in the liquid pool portion and the strain rate of 3.14 s ⁻¹ .

Further, by controlling the viscoelasticity at 25° C., which is near room temperature, it is possible to lower the adhesiveness of the coating liquid containing reinforcing fiber tape. As a result, it is possible to prevent the coating liquid-containing reinforcing fiber tape from sticking to rolls and guides in the manufacturing process, and there is also an advantage that the process can be stabilized. Furthermore, this not only makes it possible to wind the coating liquid-containing reinforcing fiber tape directly without using a release tape or the like, but also improves the unwindability of the wound coating liquid-containing reinforcing fiber tape, High-speed unwinding becomes possible. This is preferable when the coating liquid-containing reinforcing fiber tape is used as a prepreg tape because high-speed laminating with an automatic laminating device or the like becomes possible. Further, since the release tape is not used together, the amount of the prepreg tape per winding package is increased, and the operating time of the automatic laminating apparatus can be lengthened, so that the laminating efficiency in a long time is improved, which is preferable. The same effect can be obtained not only in an automatic laminating apparatus such as an AFP for aircraft, but also in a tow prepreg winding apparatus such as for a pressure tank.

Specifically, the viscosity measured at 25° C. and a strain rate of 3.14 s ⁻¹ is preferably 10 Pa·s or less, or 10 ⁶ Pa·s or more.

<Coating process by running the reinforcing fiber tape vertically downward>
A coating process will be described with reference to FIG. 1a by taking a UD substrate as an example. A method of applying the coating liquid 2 to the reinforcing fiber tape 1a in the coating apparatus 100 is a plurality of reinforcing fibers unwound from a creel 11. After arranging 1 in one direction (depth direction of paper surface) by the arranging device 12 to obtain the reinforcing fiber tape 1a, the coating liquid 2 is applied to both surfaces of the reinforcing fiber tape 1a. Thereby, the coating liquid-containing reinforcing fiber tape 1b can be obtained.

Next, the step of applying the coating liquid 2 to the reinforcing fiber tape 1a will be described in detail with reference to FIGS. FIG. 2a is an enlarged detailed cross-sectional view of the coating unit 20 in FIG. The coating part 20 is provided with wall surface members 21a and 21b that face each other with a predetermined gap D therebetween, and a cross-sectional area is continuous in the vertical downward direction Z (that is, the running direction of the reinforcing fiber tape) between the wall surface members 21a and 21b. Smaller than the cross-sectional area of the liquid pool portion 22 that is reduced in quantity and the lower surface of the liquid pool portion 22 (the unloading side of the reinforcing fiber sheet 1a) and the upper surface of the liquid pool portion 22 (the introduction side of the reinforcing fiber tape 1a). A slit-shaped narrowed portion 23 having a cross-sectional area is formed. In FIG. 2a, the reinforcing fiber tapes 1a are arranged in the depth direction of the paper surface. That is, the width direction of the reinforcing fiber tape matches the depth direction of the paper surface.

In the coating section 20, the reinforcing fiber tape 1a introduced into the liquid pool section 22 travels vertically downward Z while being accompanied by the coating liquid 2 around it. At that time, since the cross-sectional area of the liquid pool 22 decreases in the vertical downward direction Z (the traveling direction of the reinforcing fiber sheet 1a), the accompanying coating liquid 2 is gradually compressed to the lower part of the liquid pool 22. Along with this, the pressure of the coating liquid 2 increases. When the pressure in the lower part of the liquid pool portion 22 becomes higher, the associated liquid flow becomes more difficult to flow to the lower part, flows toward the wall surface members 21a and 21b, and then is blocked by the wall surface members 21a and 21b, and flows upward. Like As a result, in the liquid pool portion 22, a circulating flow T is formed along the flat surface of the reinforcing fiber tape 1a and the wall surface members 21a and 21b. As a result, even if the reinforcing fiber tape 1a brings the fluff into the liquid reservoir 22, the fluff moves along the circulation flow T and cannot approach the lower portion of the liquid reservoir 22 or the narrowed portion 23 where the liquid pressure is large. Further, as will be described below, the bubbles adhere to the fluff, so that the fluff moves upward from the circulation flow T and passes near the upper liquid surface of the liquid reservoir 22. Therefore, not only is it possible to prevent the fluff from clogging the lower portion of the liquid reservoir 22 and the narrowed portion 23, but it is also possible to easily collect the remaining fluff from the upper liquid surface of the liquid reservoir 22. Further, when the reinforcing fiber tape 1a is run at a high speed, the liquid pressure further increases, so that the effect of eliminating fluff becomes higher. As a result, it becomes possible to apply the coating liquid 2 with the reinforcing fiber tape 1a at a high speed, and the productivity is greatly improved.

Further, the increased liquid pressure has an effect of making it easier for the coating liquid 2 to be impregnated into the reinforcing fiber tape 1a. This is based on the property (Darcy's law) that the degree of impregnation increases with the pressure of the matrix resin when the matrix resin is impregnated into a porous body such as a reinforced fiber bundle. Also in this case, when the reinforcing fiber tape 1a is run at a higher speed, the liquid pressure is further increased, so that the impregnation effect can be further enhanced. The coating liquid 2 is impregnated by air/liquid substitution with the air bubbles remaining inside the reinforcing fiber tape 1a, but the air bubbles pass through the gaps inside the reinforcing fiber tape 1a due to the liquid pressure and buoyancy, and It is discharged in the orientation direction (vertically upward). At this time, the bubbles are discharged without pushing away the impregnating coating liquid 2, which also has the effect of not impeding the impregnation. Further, some of the bubbles are discharged from the surface of the reinforcing fiber tape 1a in the out-of-plane direction (normal direction), but these bubbles are also promptly removed upward in the vertical direction by the hydraulic pressure and buoyancy, so that the impregnation is performed. There is also an effect that the bubbles are not efficiently stayed in the lower portion of the liquid pool 22 and the bubbles are efficiently discharged. Due to these effects, it becomes possible to efficiently impregnate the reinforced fiber tape 1a with the coating liquid 2, and as a result, it is possible to obtain a high-quality coating liquid-containing reinforced fiber tape 1b in which the coating liquid 2 is uniformly impregnated. Becomes

Further, due to the increased hydraulic pressure, the reinforcing fiber tape 1a is automatically centered in the center of the gap D, and the reinforcing fiber tape 1a does not directly rub against the wall surfaces of the liquid reservoir 22 and the narrowed portion 23. It also has the effect of suppressing the generation of fluff. This is because when the reinforcing fiber tape 1a approaches either of the gaps D due to disturbance or the like, the coating liquid 2 is pushed into a narrower gap on the approaching side and is compressed, so that the liquid pressure increases on the approaching side. The reason is that the reinforcing fiber tape 1a is pushed back to the center of the gap D.

The narrowed portion 23 is designed to have a smaller cross-sectional area than the upper surface of the liquid reservoir 22. As can be seen from FIG. 2a, the length of the quasi-plane formed by the reinforcing fiber sheet in the direction of the normal is small, that is, the distance between the members is small, and thus the cross-sectional area is small. This is to obtain the impregnation and self-centering effects by increasing the liquid pressure in the narrowed portion as described above. From the viewpoint of running property of the reinforcing fiber tape 1a and flow control of the coating liquid 2, it is necessary that the cross-sectional shape of the uppermost surface of the narrowed portion 23 matches the cross-sectional shape of the lowermost surface of the liquid reservoir 22. Although preferable, the narrowed portion 23 may be made slightly larger than necessary.

Here, in the application section 20 of FIG. 2a, the reinforcing fiber tape 1a runs completely downward in the vertical direction Z (90 degrees from the horizontal plane), but the present invention is not limited to this, and the fluff collection and bubble discharge effects described above are possible. Is obtained, and the reinforcing fiber tape 1a may be directed downward in the vertical direction within a range in which stable and continuous running is possible.

Further, the total amount of the coating liquid 2 applied to the reinforcing fiber tape 1a can be controlled by the gap D of the narrowed portion 23, and for example, it is desired to increase the total amount of the coating liquid 2 applied to the reinforcing fiber tape 1a (a large basis weight is used). If desired), the wall surface members 21a and 21b may be installed so that the gap D becomes wide.

FIG. 1c shows an example in which the reinforcing fiber tape 1a is made of carbon fiber and is equipped with a firing device 11a. In this example, the firing step and the coating step are continuously performed, and the reinforcing fiber tape 1a runs downward in the vertical direction.

Further, as will be described later, in the coating section 20, the reinforcing fiber tape 1a can be passed in a substantially horizontal direction or an inclined direction. Whether to pass the reinforcing fiber tape 1a in the vertically downward direction, in the horizontal direction, or in the inclined direction can be determined depending on, for example, the space for installing the device and the relationship with the front and rear processes.

<Application process by running the reinforcing fiber tape in the horizontal direction or the inclined direction>
The process of applying the matrix resin when the reinforcing fiber tape 1a runs in the horizontal direction or the inclined direction will be described with reference to FIG. 1b. The method for applying the matrix resin 2 to the reinforcing fiber sheet 1a in the coating apparatus 100 is a creel. After arranging the plurality of reinforcing fibers 1 unwound from 11 in one direction (depth direction of the paper surface) by the arranging device 12 to obtain the reinforcing fiber tape 1a, the reinforcing fiber tape 1a is passed through the coating section 20 in the horizontal direction or the inclined direction. Then, the matrix resin 2 is applied to both surfaces of the reinforcing fiber sheet 1b. Here, the horizontal direction refers to the X direction in FIG. 1b, and the tilt direction refers to an intermediate azimuth between the X direction and the Z direction in FIG. 1b. In addition, when the reinforcing fiber sheet 1a is introduced horizontally with respect to the application portion 20 as shown in FIG. 1b, the traveling path of the reinforcing fiber sheet 1a is linearized, and the reinforcing fiber sheet 1a is disturbed due to the thickness of the reinforcing fiber sheet 1a. Is less likely to occur, which is preferable. At this time, it is preferable to have a sealing mechanism that prevents the matrix resin 2 from leaking at the introduction portion of the reinforcing fiber sheet 1a into the coating portion 20.

FIG. 1d shows an example in which the reinforcing fiber tape 1a is made of carbon fiber and is equipped with a firing device 11a. In this example, the firing step and the coating step are continuously performed, and the reinforcing fiber tape 1a runs in the horizontal direction.

Next, the step of applying the coating liquid 2 to the carbon fiber tape when the reinforcing fiber tape 1b runs in the horizontal direction or the inclined direction will be described in detail with reference to FIGS. FIG. 2b is an enlarged detailed cross-sectional view of the coating section 20 in FIG. 1b. The coating part 20 is provided with wall surface members 21a and 21b which face each other with a predetermined gap D therebetween, and the wall surface members are integrated on the introduction side and the outlet side of the reinforcing fiber tape 1b. Between the upper surface wall member 21a and the lower wall member 21b, there is a liquid pool portion 22, and a slit-like portion located on the outlet side of the liquid pool portion 22 and having a cross-sectional area smaller than the maximum portion of the liquid pool portion 22. A narrowed portion 23 is formed.

In the coating section 20, the reinforcing fiber tape introduced into the liquid pool section 22 travels in the horizontal direction while accommodating the coating liquid 2 around it. At that time, as in the case of running the reinforcing fiber tape downward in the vertical direction, in the area 22b of the liquid pool portion 22 where the cross-sectional area continuously decreases in the running direction of the reinforcing fiber tape, the coating that is accompanied. The liquid 2 is gradually compressed, and the pressure of the coating liquid 2 increases toward the outlet of the liquid reservoir 22. When the pressure in the vicinity of the outlet of the liquid pool portion 22 becomes higher, it becomes difficult for the associated liquid flow to flow further in the outlet direction, and it flows in the direction perpendicular to the reinforcing fiber tape, and then the wall members 21a and 21b are blocked. In rare cases, it flows in the direction opposite to the running direction of the reinforcing fiber tape. As a result, in the liquid pool 22, a circulating flow T is formed along the flat surface of the reinforcing fiber tape and the wall surface of the wall member 21a and the wall member 21b. As a result, even if the reinforcing fiber tape brings the fluff into the liquid reservoir 22, the fluff moves along the circulation flow T and cannot approach the vicinity of the outlet of the liquid reservoir 22 or the narrowed portion 23 where the liquid pressure is high. When the running speed of the reinforcing fiber tape is increased, the liquid pressure is further increased, so that the effect that the fluff cannot approach the vicinity of the outlet or the narrowed portion 23 becomes higher, and the productivity is greatly improved.

Further, as in the case of running the reinforcing fiber tape downward in the vertical direction, there is an effect that the coating liquid 2 is easily impregnated into the reinforcing fiber tape due to the increased liquid pressure. This is based on the property (Darcy's law) that when a porous material such as a carbon fiber bundle is impregnated with a matrix resin, the degree of impregnation increases with the pressure of the matrix resin. Also in this case, when the reinforcing fiber tape 1b is run at a higher speed, the liquid pressure is further increased, so that the impregnation effect can be further enhanced. The coating liquid 2 is impregnated with the air bubbles remaining inside the reinforcing fiber tape by gas/liquid exchange. However, the air bubbles continuously flow in the cross-sectional area 22a where the cross-sectional area does not decrease due to the circulation flow T and buoyancy. A large number will be gathered near the boundary of the decreasing region 22b. Therefore, it is preferable to install a degassing mechanism 56 for degassing bubbles from the coating liquid 2 in the vicinity of this.

Furthermore, as in the case of running the reinforcing fiber tape downward in the vertical direction, the reinforcing liquid tape is automatically centered in the center of the gap D by the increased liquid pressure, and the reinforcing fiber tape is collected in the liquid pool 22 or It does not directly rub against the wall surface of the narrowed portion 23, and also has an effect of suppressing the generation of fluff here. This is because when the reinforcing fiber tape approaches either of the gaps D due to disturbance or the like, the matrix resin 2 is pressed into a narrower gap on the approaching side and is compressed, so that the liquid pressure increases on the approaching side. This is because the reinforcing fiber tape is pushed back to the center of the gap D.

The narrowed portion 23 is designed to have a smaller cross-sectional area than the maximum portion of the liquid reservoir 22. As can be seen from FIG. 2b, the length of the quasi-plane formed by the reinforcing fiber tape in the perpendicular direction is small, that is, the interval between the members is small, and thus the cross-sectional area is small. This is to obtain the impregnation and self-centering effects by increasing the liquid pressure in the narrowed portion 23 as described above. Further, it is preferable that the cross-sectional shape of the inlet portion of the narrowed portion 23 is matched with the cross-sectional shape of the surface of the liquid pool portion 22 that is in contact with the narrowed portion 23 from the viewpoint of the running property of the reinforcing fiber tape 1b and the flow control of the matrix resin 2. If necessary, the narrowed portion 23 may be made slightly larger.

Here, although the reinforcing fiber tape runs in the horizontal direction completely in the coating section 20 of FIG. 2B, the present invention is not limited to this, and the above-mentioned fluff collection and air bubble discharging effects are obtained, and the carbon fiber sheet 1a is obtained. May travel in the inclining direction within the coating section 20 within a range in which stable running is possible. It is also possible to incline the application part 20.

Further, the total amount of the coating liquid 2 applied to the reinforcing fiber tape can be controlled by the gap D of the narrowed portion 23, as in the case of running the reinforcing fiber tape downward in the vertical direction. When it is desired to increase the total amount of the coating liquid 2 to be applied (to increase the basis weight), the gap D may be adjusted to be wide.

Although FIG. 2b illustrates a case where one reinforcing fiber tape is introduced from the horizontal direction to the application part, the introduction of the reinforcing fiber tape to the application part is not limited to this, and if necessary, a plurality of reinforcing fiber tapes may be used. Alternatively, the introduction direction may be an inclined direction. This will be described with reference to FIGS.

In FIG. 2 c, one sheet of reinforcing fiber tape 1 a runs obliquely downward from above and is introduced into the coating section 20 through the opening 60. The direction of the reinforcing fiber tape 1a is changed to the horizontal direction by the direction changing member 61, and the reinforcing fiber tape 1a is pulled out from the narrowed portion 23. Here, it is preferable that at least the surface of the direction changing member 61, which is in contact with the reinforcing fiber tape 1a, has a curved surface. Further, from the viewpoint of preventing the reinforcing fiber tape 1a from winding around, it is preferable that the direction changing member 61 is fixed. From these, the direction changing portion 61 is preferably a fixed bar having a curved surface, and the cross-sectional shape thereof may be circular, elliptical, saddle-shaped or the like. Further, a curved surface and a flat surface may be mixed in a portion where the direction changing member 61 and the reinforcing fiber tape 1a are in contact with each other. However, when the grounding start portion and the end portion of the reinforcing fiber tape 1a are curved surfaces, generation of fluff can be suppressed. ,preferable. Further, particularly in the case of increasing the traveling speed, from the viewpoint of suppressing the rubbing between the reinforcing fiber tape 1a and the direction changing member 61, it is possible to use a rotatable roller.

Further, since the reinforcing fiber tape 1a is pressed against the direction changing member 61, impregnation may be performed by replacing the gas in the reinforcing fiber tape 1a with the coating liquid 2. In particular, as shown in FIG. 2e, the impregnation can be proceeded more efficiently by abutting the plurality of direction changing members 61 at an angle.

Further, the installation position of the direction changing member 61 is 1 cm or more from the boundary position of the region 22a where the cross-sectional area does not decrease and the region 22b where the cross-sectional area continuously decreases, from the viewpoint of not impeding the flow of the circulation flow T, and the cross-sectional area is 1 cm or more. It is preferable that the area 22a is not reduced.

In FIG. 2 d, two reinforcing fiber tapes 1 a run obliquely downward from above and are introduced into the coating section 20 through the opening 60. Then, the two reinforcing fiber tapes 1a are each changed in the traveling direction to the horizontal direction by the direction changing member 61, and after the two sheets are laminated, they are pulled out from the narrowed portion 23. At this time, since the matrix resin 2 is contained and laminated between the two reinforcing fiber tapes 1a, impregnation is more likely to proceed in the region 22b and the narrowed portion 23 where the cross-sectional area continuously decreases, which is preferable.

In FIG. 2 e, two reinforcing fiber tapes 1 a run obliquely downward from the top and are introduced into the coating part 20 through the opening 60. Then, the two reinforcing fiber tapes 1a are impregnated while passing through the plurality of direction changing members 61, respectively, and finally two sheets are laminated and then pulled out from the narrowed portion 23. At this time, the shape and number of the direction changing members 61 for advancing the impregnation can be variously selected according to the purpose. Further, the contact length between the direction changing member 61 and the reinforcing fiber tape 1a and the wrap angle formed by both ends of the contact part and the center of the direction changing member 61 can be selected according to the purpose.

2d and 2e show an example in which the number of the reinforcing fiber tapes 1a is two, but of course, the number of the reinforcing fiber tapes 1a can be any number of three or more.

FIG. 3 is a bottom view of the coating section 20 seen from the direction A in FIG. 2A. The coating section 20 is provided with side wall members 24a and 24b for preventing the coating liquid 2 from leaking from both ends of the reinforcing fiber tape 1a in the arrangement direction, and is surrounded by the wall surface members 21a and 21b and the side wall members 24a and 24b. An outlet 25 of the narrowed portion 23 is formed in the open space. Here, the outlet 25 has a slit shape, and the cross-sectional aspect ratio (U/D in FIG. 3) may be set according to the shape of the reinforcing fiber tape 1a to which the coating liquid 2 is desired to be applied.

FIG. 4A is a cross-sectional view illustrating the internal structure of the coating section 20 when the coating section 20 is viewed from the direction B. In addition, the wall member 21b is omitted in order to make the drawing easier to see, and the reinforcing fiber tape 1a is drawn so that the reinforcing fibers 1 are arranged with a gap therebetween. Arranging without gaps is preferable from the viewpoint of the quality of the prepreg tape (an aspect of the coating liquid-containing reinforcing fiber tape) and the mechanical properties of the FRP obtained by molding the prepreg tape.

FIG. 4 b shows the flow of the coating liquid 2 in the gap 26. When the gap 26 is large, a swirl flow is generated in the coating liquid 2 in the R direction. This vortex flow R becomes a flow (Ra) toward the outside in the lower part of the liquid pool portion 22, so that the reinforcing fiber tape may be torn (cracking) or the space between the reinforcing fibers may be widened, and When the coating liquid-containing reinforcing fiber tape is used, the reinforcing fibers may be unevenly arranged. On the other hand, in the upper part of the liquid pool 22, the flow (Rb) is directed inward, so that the reinforcing fiber tape 1a may be compressed in the width direction and its end may be broken. Such a vortex flow is generated in the gap 26 in an apparatus such as that disclosed in Patent Document 2 (Japanese Patent No. 3252278), which applies the coating liquid to both sides of a monolithic sheet-shaped substrate (especially a film). However, attention was not paid because it had little effect on quality.

Therefore, in the present invention, it is preferable to control the width to reduce the gap 26 and suppress the generation of the vortex flow at the end portion. Specifically, the width L (mm) of the liquid reservoir 22, that is, the distance L (mm) between the side plate members 24a and 24b is equal to or less than the width W (mm) of the reinforcing fiber tape measured immediately below the narrowed portion 23. It is preferable that the above-mentioned relationship be satisfied.
L≦1.1×W.

As a result, generation of vortex flow at the ends can be suppressed, cracks and breaks at the ends of the reinforcing fiber tape 1a can be suppressed, and the reinforcing fibers 1 are arranged uniformly over the entire width (W) of the coating liquid containing reinforcing fiber tape 1b. Thus, it is possible to obtain the coating liquid-containing reinforcing fiber tape 1b having high quality and high stability. Furthermore, when this technique is applied to a prepreg tape, not only the quality and quality of the prepreg tape can be improved, but also the mechanical characteristics and quality of the FRP obtained by using this can be improved.

Moreover, it is preferable to adjust the lower limit of L to be 0.9×W or more. In this way, controlling the distance L between the side plate members 24a and 24b is also preferable from the viewpoint of improving the dimensional accuracy in the width direction of the coating liquid containing reinforcing fiber tape 1b.

The width regulation is preferably performed at least in the lower part of the liquid pool 22 (position G in FIG. 4a) from the viewpoint of suppressing the generation of the vortex flow R due to the high liquid pressure in the lower part of the liquid pool 22. Furthermore, if this width regulation is more preferably performed in the entire area of the liquid pool portion 22, the generation of the vortex flow R can be almost completely suppressed, and as a result, cracking of the reinforcing fiber tape and breakage of the end portion can be almost completely suppressed. Can be suppressed.

Further, the width regulation may be performed only on the liquid pool portion 22 from the viewpoint of suppressing the vortex flow in the gap 26, but if the narrowing portion 23 is also performed in the same manner, an excessive amount of coating liquid on the side surface of the coating liquid-containing reinforcing fiber tape 1b may be applied. It is preferable from the viewpoint of suppressing the addition of 2.

<Width control mechanism>
Although the case where the side wall members 24a and 24b bear the width regulation has been described above, as shown in FIG. 5a, the width regulation mechanism 27a and 27b may be provided between the side wall members 24a and 24b, and the width regulation may be performed by such a mechanism. it can. Thus, the width regulated by the width regulating mechanism can be freely changed, which is preferable from the viewpoint that the coating liquid-containing reinforced fiber tapes having various widths can be manufactured by one coating section. Here, the relationship between the width W (mm) of the reinforcing fiber tape immediately below the narrowed portion and the width L2 (mm) regulated by the width regulating mechanism at the lower end of the width regulating mechanism is L2≦1.1×W. Is preferred. Further, the lower limit of L2 can be adjusted to be 0.9×W or more. In this way, controlling the width L2 regulated by the width regulating mechanism is preferable also from the viewpoint of improving the dimensional accuracy in the width direction of the coating liquid-containing reinforcing fiber tape 1b.

The shape and material of the width regulating mechanism are not particularly limited, but a plate-shaped bush is simple and preferable. Also, at the upper portion, that is, at a place near the liquid surface, a width smaller than the distance between the wall surface members 21a and 21b (see FIG. 5a. In the “view from the Z direction”, refers to the vertical length of the width regulating mechanism). By having it, it is possible to prevent the horizontal flow of the coating liquid from being hindered, which is preferable. On the other hand, from the middle part to the lower part of the width regulation mechanism, it is preferable to have a shape that conforms to the internal shape of the coating part because it is possible to suppress the retention of the coating liquid in the liquid reservoir and to suppress the deterioration of the coating liquid. From this point of view, the width regulating mechanism is preferably inserted up to the narrowed portion 23. FIG. 5A shows an example of a plate-shaped bush as the width regulating mechanism, but shows an example in which the lower part from the middle of the bush is inserted along the tapered shape of the liquid reservoir 22 up to the narrowed part 23. Although FIG. 5a shows an example in which L2 is constant from the liquid surface to the outlet, the width to be regulated by the portion may be changed within the range in which the purpose of the width regulation mechanism is achieved. The width regulating mechanism can be fixed to the coating section 20 by an arbitrary method. However, in the case of a plate-shaped bush, by fixing it at a plurality of parts in the vertical direction, the plate-shaped bush is restricted by deformation of the plate-shaped bush due to high hydraulic pressure. Variation in width can be suppressed. For example, it is preferable to use a stay for the upper part and insert the lower part for the coating part because the width can be easily regulated by the width regulating mechanism.

<Width accuracy of reinforced fiber tape containing coating liquid>
As described above, in the present invention, it is possible to improve the running stability of the reinforcing fiber tape by various width restrictions in the coating step, but similarly, it is also possible to improve the width accuracy of the coating liquid containing reinforcing fiber tape. .. More specifically, the variation coefficient (CV) of the coating liquid-containing reinforcing fiber tape width is 5% or less.

The coefficient of variation (CV) of the tape width can be obtained as follows. First, the width (W _n ) of the coating liquid containing reinforcing fiber tape is measured at 30 points or more in the tape longitudinal direction. As a width measuring method, the coating liquid containing reinforcing fiber tape obtained may be measured discretely by using a caliper or the like. Can also be measured with a caliper. Also at this time, the measurement is performed discretely. In the case of discrete measurement, the distance between measurement points should be 30 cm or more in the tape longitudinal direction. In addition, an optical width measuring device may be installed below the coating section to continuously measure the width. Examples of the width measuring device include LS-7030 manufactured by Keyence Corporation. In the case of continuous measurement, 10 m or more is measured in the tape longitudinal direction, and data (W _n ) of 30 points or more is acquired. The average value of the tape width from these measured values _{(W n) (W} A), a standard deviation (sigma _W), can be obtained (1) wide variation coefficient from the equation (CV).
CV(%)=(σ _W /W _A )×100(%) (1).

In the method using a kiss roll as in Patent Document 5, since the reinforcing fiber tape has no width regulation on the roll for applying the coating liquid, the reinforcing fiber easily moves in the width direction due to the permeation of the coating liquid, and the width is essentially reduced. Is likely to fluctuate. Actually, in Patent Document 5, the width regulating roll is made to act after the resin is applied by the kiss roll, which is considered to indicate that the width accuracy on the kiss roll which is the application portion is insufficient. On the other hand, in the present invention, since the tape width can be controlled at the coating portion by controlling the width L of the liquid pool portion or adding the width regulation mechanism as described above, such a high tape width accuracy can be obtained. Be done. When the width regulation is performed after the matrix resin is applied as in Patent Document 5, it is predicted that extra matrix resin adheres to the width regulation portion to cause problems such as destabilizing the process and shortening the cleaning cycle. It On the other hand, when the width is regulated in the coating section as in the present invention, the coating liquid (matrix resin or the like) applied after the width is regulated can be measured, so that the possibility that the excess coating liquid will contaminate the downstream of the process is low. Is also an advantage.

<Cooling immediately after coating>
As shown in FIG. 5b, it is possible to cool the coating liquid-containing reinforcing fiber tape by performing a cooling step subsequent to the coating step. Here, that the coating step and the cooling step are continuous means that each step is performed without the presence of other devices such as the transport roll 14 between the apparatus that performs the coating step and the apparatus that performs the cooling step. Cooling the coating liquid containing reinforcing fiber tape immediately after coating increases the viscosity of the resin impregnated in the reinforcing fiber tape and suppresses resin flow in the reinforcing fiber tape to maintain good width accuracy. It is possible to The distance between the coating unit 20 and the cooling device 62 is not particularly limited, but the closer the distance, the higher the effect, and the distance is preferably 500 mm or less. The form of the cooling device is not particularly limited, and examples thereof include a method in which air having a temperature lower than that of the coating liquid in the liquid reservoir is applied to the coating liquid-containing reinforcing fiber tape.

<Shape of liquid pool>
As described above in detail, in the present invention, the liquid pool portion 22 continuously decreases the cross-sectional area in the running direction of the reinforcing fiber tape, thereby increasing the hydraulic pressure in the running direction of the reinforcing fiber tape. Importantly, the fact that the cross-sectional area continuously decreases in the running direction of the reinforcing fiber tape is not particularly limited as long as the hydraulic pressure can be continuously increased in the running direction. In the cross-sectional view of the liquid pool portion, it may have a tapered shape (straight line shape) or a curved shape such as a trumpet shape. Further, the cross-sectional area reduction portion may be continuous over the entire length of the liquid pool portion, and within a range where the object and effect of the present invention can be obtained, a portion including a portion where the cross-sectional area is not reduced or a portion where the cross-sectional area is enlarged is included You can leave. These will be described in detail below with reference to examples in FIGS.

FIG. 6 is a detailed cross-sectional view of the coating unit 20b of another embodiment different from FIG. It is the same as the coating unit 20 of FIG. 2 except that the wall members 21c and 21d forming the liquid pool 22 have different shapes. Like the coating portion 20b in FIG. 6, the liquid pool portion 22 may be divided into a region 22a in which the cross-sectional area continuously decreases in the vertical downward direction Z and a region 22b in which the cross-sectional area does not decrease. At this time, the vertical height H at which the cross-sectional area continuously decreases is preferably 10 mm or more. A more preferable vertical height H at which the cross-sectional area continuously decreases is 50 mm or more. As a result, the coating liquid 2 entrained by the reinforcing fiber tape 1a has a sufficient distance to be compressed in the region 22a where the cross-sectional area of the liquid reservoir 22 continuously decreases, and the liquid generated in the lower portion of the liquid reservoir 22 is secured. The pressure can be increased sufficiently. As a result, it is possible to prevent the fluff from being clogged in the narrowed portion 23 due to the liquid pressure, and to obtain the effect of impregnating the reinforcing fiber tape 1a with the coating liquid 2 due to the liquid pressure.

Here, when the area 22a in which the cross-sectional area of the liquid reservoir 22 continuously decreases is tapered like the coating section 20 of FIG. 2 and the coating section 20b of FIG. 6, the taper opening angle θ is smaller. Is preferable, and specifically, an acute angle (90° or less) is preferable. As a result, the compression effect of the matrix resin 2 can be enhanced in the region 22a (tapered portion) where the cross-sectional area of the liquid reservoir 22 is continuously reduced, and high liquid pressure can be easily obtained.

FIG. 7 is a detailed cross-sectional view of the coating unit 20c of another embodiment different from FIG. The coating part 20b is the same as the coating part 20b in FIG. 6 except that the wall surface members 21e and 21f forming the liquid pool 22 have a two-step taper shape. As described above, the region 22a in which the cross-sectional area of the liquid pool portion 22 continuously decreases may be configured by a multi-step tapered portion having two or more steps. At this time, it is preferable to set the opening angle θ of the tapered portion closest to the narrowed portion 23 to an acute angle from the viewpoint of enhancing the compression effect. Also in this case, it is preferable that the height H of the region 22a where the cross-sectional area of the liquid reservoir 22 continuously decreases is 10 mm or more. A more preferable vertical height H at which the cross-sectional area continuously decreases is 50 mm or more. As shown in FIG. 7, the region 22a where the cross-sectional area of the liquid reservoir 22 continuously decreases is made into a multi-step taper portion, so that the narrowed portion 23 can be maintained while maintaining the volume of the coating liquid 2 that can be stored in the liquid reservoir 22. It is possible to further reduce the angle θ of the tapered portion closest to As a result, the liquid pressure generated in the lower portion of the liquid reservoir 22 becomes higher, and the effect of eliminating fluff and the effect of impregnating the coating liquid 2 can be further enhanced.

FIG. 8 is a detailed cross-sectional view of the coating unit 20d of another embodiment different from that of FIG. 6 is the same as the coating unit 20b in FIG. 6 except that the wall members 21g and 21h forming the liquid pool 22 have a stepped shape. As described above, if the lowermost portion of the liquid pool 22 has the region 22a where the cross-sectional area continuously decreases, the effect of increasing the hydraulic pressure, which is the object of the present invention, can be obtained. May include a region 22c whose cross-sectional area decreases intermittently. By forming the liquid pool portion 22 into the shape as shown in FIG. 8, the depth B of the liquid pool portion 22 can be increased and stored while maintaining the shape of the region 22a in which the cross-sectional area continuously decreases. The volume can be increased. As a result, even when the coating liquid 2 cannot be continuously supplied to the coating unit 20d, the coating liquid 2 can be continuously applied to the reinforcing fiber tape 1a for a long time, and the productivity of the coating liquid-containing reinforcing fiber tape 1b is improved. To improve.

FIG. 9 is a detailed cross-sectional view of the coating unit 20e of another embodiment different from FIG. 6 is the same as the coating unit 20b in FIG. 6 except that the wall surface members 21i and 21j forming the liquid pool 22 have a trumpet shape (curved shape). In the coating part 20b of FIG. 6, the region 22a in which the cross-sectional area of the liquid pool part 22 continuously decreases is a taper shape (linear shape), but is not limited to this, for example, a trumpet shape (curved shape) as shown in FIG. But it's okay. However, it is preferable that the lower portion of the liquid reservoir 22 and the upper portion of the narrowed portion 23 are smoothly connected. This is because if there is a step at the boundary between the lower portion of the liquid reservoir 22 and the upper portion of the narrowed portion 23, the reinforcing fiber sheet 1a may be caught in the step and fluff may be generated at this portion. Further, when the region where the cross-sectional area of the liquid pool 22 continuously decreases is formed into a trumpet shape, the opening of the imaginary tangent line at the bottom of the region 22a where the cross-sectional area of the liquid pool 22 continuously decreases. It is preferable that the angle θ be acute.

In the above description, the cross-sectional area is smoothly reduced, but the cross-sectional area of the liquid reservoir does not necessarily have to be reduced smoothly in the present invention as long as the object of the present invention is not impaired.

FIG. 10 is a detailed cross-sectional view of the coating unit 30 according to another embodiment of the present invention. Unlike the embodiment of the present invention, the liquid pool portion 32 of FIG. 10 does not include a region where the cross-sectional area continuously decreases in the vertical downward direction Z, and the cross-sectional area at the boundary 33 with the narrowed portion 23 is discontinuous and sharp. It is a structure that reduces to. Therefore, the reinforcing fiber tape 1a is likely to be clogged.

Further, it is possible to improve the impregnation effect by bringing the reinforcing fiber tape into contact with a plurality of bars in the coating section. FIG. 11 shows an example in which three bars (35a, 35b and 35c) are used. The larger the number of bars, the longer the contact length between the reinforcing fiber tape and the bar, the larger the contact angle, the impregnation rate. Can be improved. In the example of FIG. 11, the impregnation rate can be 90% or more. The means for improving the impregnation effect may be used in combination of plural kinds.

<Resin film application process>
In the present invention, a resin film may be further applied to the coating liquid-containing reinforcing fiber tape 1b drawn out from the coating step. Referring to FIG. 1, a resin film can be supplied from the supply device 16 instead of the release tape 3 and laminated on the coating liquid-containing reinforcing fiber tape 1b on the transport roll 14. In FIG. 1, the number of resin films is one, but it is of course possible to apply resin films from both sides of the coating liquid containing reinforcing fiber tape 1b, or either one may be used as a release film. When two resin films are used, they may be the same resin film or different types of resin films. The resin film may be coated on a support such as a release tape, or may not include the support.

In the present invention, the resin used for the resin film is not particularly limited and can be appropriately selected according to the purpose. The resin used as the resin film may be a single resin, a blend of different polymers, or a resin composition that is a blend of various components. The resin film used here may contain the particles. If a matrix resin containing particles is used as a coating liquid in the coating step, the viscosity tends to increase, and the coating uniformity may deteriorate when the reinforcing fiber sheet runs at high speed. Therefore, it is preferable to add particles in the resin film applying step because the high speed running stability of the reinforcing fiber tape in the applying step is improved. At this time, the resin film containing particles may be a resin film made of a matrix resin. By doing so, the matrix resin can be applied while the particles are applied separately from the coating step, which is efficient. At this time, the matrix resin of the matrix resin containing particles may be the same as or different from the matrix resin component used in the coating step. The components of the matrix resin used in the coating step and the matrix resin forming a resin film can be adjusted in consideration of the high-speed running stability in the coating step and the pot life in storage in the coating section.

It is also possible to take out a certain resin component from the matrix resin and form this into a resin film. For example, in FRP, a thermoplastic resin can be blended with a matrix resin mainly composed of a thermosetting resin to improve the resin toughness, but this thermoplastic resin may increase the matrix resin viscosity. In such a case, the coating stability can be improved by removing the thermoplastic resin from the matrix resin applied in the applying step and applying it as a resin film to the coating liquid-containing reinforcing fiber tape. As such a thermoplastic resin, PES, PEI, PI, etc. are often used. In addition, such a thermoplastic resin film may be a self-supporting film that does not require a support, which is useful from the viewpoint of omitting the support.

A known method can be used for producing the resin film, and for example, a film can be formed using various known coaters such as a roll coater, a comma coater, a knife coater, a die coater, and a spray coater. If necessary, a resin may be coated on a support such as a release sheet to form a film.

<Travel mechanism>
A known roller or the like can be preferably used as a running mechanism for conveying the reinforcing fiber tape or the coating liquid-containing reinforcing fiber tape. In the present invention, since the reinforcing fiber tape is conveyed vertically downward, it is preferable to arrange the rollers above and below with the application section sandwiched therebetween.

Further, in the present invention, it is preferable that the running path of the reinforcing fiber tape is as linear as possible in order to suppress the disorder of arrangement of the reinforcing fibers and fuzzing. In addition, the coating liquid-containing reinforcing fiber tape is often a sheet-like integrated body that is a laminate with a release tape. However, if a bent portion is provided in the transporting process of the release tape, wrinkles due to a difference in circumferential length between the inner layer and the outer layer are caused. Therefore, it is preferable that the traveling path of the sheet-like integrated body be linear as much as possible. From this point of view, it is preferable to use a nip roll in the traveling path of the sheet-shaped integrated body.

Whether to use the S-shaped roll or the nip roll can be appropriately selected according to the manufacturing conditions and the characteristics of the product.

<High tension take-up device>
In the present invention, it is preferable to dispose a high tension take-up device for pulling out the coating liquid-containing reinforcing fiber tape from the coating section, downstream of the coating section. This is because high frictional force and shear stress are generated between the reinforcing fiber tape and the coating liquid in the coating part, and in order to overcome it and pull out the coating liquid containing reinforcing fiber tape, a high take-up tension is generated in the downstream of the process. This is because it is preferable to allow it. A nip roll or an S-shaped roll can be used as the high-tension take-up device, but in both cases, slipping is prevented and stable running is possible by increasing the frictional force between the roll and the coating liquid containing reinforcing fiber tape. Can be For this purpose, it is preferable to dispose a material having a high friction coefficient on the roll surface, or to increase the nip pressure and the pressing pressure of the coating liquid containing reinforcing fiber tape to the S-shaped roll. From the viewpoint of preventing slippage, the S-shaped roll is preferable because the frictional force can be easily controlled by the roll diameter and the contact length.

<Release tape feeder>
In the production of the coating liquid-containing reinforcing fiber tape or FRP using the present invention, a release tape feeding device can be appropriately used, and as such a known one can be used. It is preferable to have a mechanism capable of feeding back the tension to the unwinding speed from the viewpoint of stable running of the release tape.

<Additional impregnation>
In order to adjust the degree of impregnation to a desired level, it is possible to combine the present invention with a means for further increasing the degree of impregnation using an impregnating device after coating. Here, in order to distinguish it from the impregnation in the coating part, additional impregnation after coating is referred to as additional impregnation, and a device therefor is referred to as additional impregnation device. The device used as the additional impregnation device is not particularly limited and can be appropriately selected from known devices according to the purpose. For example, as described in JP2011-132389A and WO2015/060299 pamphlet, after a laminate of a sheet-shaped carbon fiber bundle and a resin is preheated with a hot plate to sufficiently soften the resin on the sheet-shaped carbon fiber bundle. The impregnation can be promoted by using a device which pressurizes with a heated nip roll. The hot plate temperature for preheating, the nip roll surface temperature, the nip roll linear pressure, and the nip roll diameter and number can be appropriately selected so as to obtain a desired impregnation degree. It is also possible to use an "S-lap roll" in which a prepreg sheet runs in an S shape as described in WO 2010/150022 pamphlet. In the present invention, the "S-wrap roll" is simply referred to as "S-shaped roll". WO2010/150022 Pamphlet FIG. 1 describes an example in which a prepreg sheet travels in an S shape, but if impregnation is possible, the contact length between the sheet and the roll, such as a U shape, a V shape, or a Λ shape. May be adjusted. Further, in the case of increasing the impregnation pressure and increasing the degree of impregnation, it is possible to add contact rolls facing each other. Further, as shown in FIG. 4 of WO2015/076981 pamphlet, it is possible to improve the impregnation efficiency by arranging a conveyor belt so as to face the "S-wrap roll", thereby increasing the production speed of the prepreg. Further, as described in WO2017/068159 pamphlet, JP-A-2016-203397, etc., it is possible to improve the impregnation efficiency by applying ultrasonic waves to the prepreg before the impregnation and rapidly raising the temperature of the prepreg. is there. Further, as described in JP-A-2017-154330, it is also possible to use an impregnating device for vibrating a plurality of "ironing blades" with an ultrasonic generator. It is also possible to fold and impregnate a prepreg as described in JP 2013-22868 A.

<Simple additional impregnation>
In the above, an example of applying the conventional additional impregnation device was shown, but the temperature of the coating liquid-containing reinforcing fiber tape may still be high just below the coating part, and in such a case, after leaving the coating part, not much. If an additional impregnation operation is added before the time has passed, a heating device such as a heating plate for reheating the coating liquid-containing reinforcing fiber tape can be omitted or simplified, and the impregnation device can be greatly simplified and downsized. It is also possible. The impregnating device positioned just below the coating unit will be referred to as a simple additional impregnating device. A heated nip roll or a heated S-shaped roll can be used as a simple additional impregnation device, but the roll diameter, set pressure, and contact length between the coating liquid-containing reinforcing fiber tape and the roll can be reduced compared to a normal impregnation device. It is preferable that not only the device can be downsized but also the power consumption can be reduced.

Further, it is preferable to apply a release tape to the coating liquid-containing reinforcing fiber tape before the coating liquid containing reinforcing fiber tape enters the simple additional impregnation device because the running property of the coating liquid containing reinforcing fiber tape is improved.

FIG. 13a shows an example of a manufacturing process of a coating liquid-containing reinforcing fiber tape equipped with an additional impregnation device. A simple additional impregnation device 453 is provided immediately below the coating unit 430. Here, the simple additional impregnation device 453 shows an example of a nip roll, but the nip roller is preferably equipped with a heating mechanism. Further, the number of nip rolls can be appropriately selected depending on the purpose, but from the viewpoint of process simplification, 3 or less is preferable (FIG. 13a shows an example of 2 stages). Further, it is preferable that the nip roller is provided with a driving device from the viewpoint of easily controlling the tension of the transport of the coating liquid-containing reinforcing fiber tape. The nip pressure can be appropriately adjusted according to the desired degree of impregnation.

Further, it is preferable that the surface of the nip roll is subjected to an appropriate release treatment so that the coating liquid-containing reinforcing fiber tape does not stick, or that a release tape is inserted between the coating liquid-containing reinforcing fiber tape and the nip roll. (Not shown in Figure 13a for simplicity). When the release sheet is inserted between the coating liquid-containing reinforcing fiber tape and the nip roll, the release sheet is inserted from the coating section 430 side, and the release tape is separated from the coating liquid-containing reinforcing fiber tape by the roll on the high tension take-up device 444 side. Preferably. The separated release tape may be wound up as it is, or may be run again on the circuit so that it may be inserted again from the coating section 430 side.

In addition to the nip roll, the above-mentioned "S-lap roll", a fixed bar, or the like can be used as the additional impregnation device.

Note that FIG. 13A shows an example in which after simple additional impregnation and application of a matrix resin film, it is guided to the additional impregnation device 450 as it is.

<Rewind>
In the present invention, the coating liquid-containing reinforcing fiber tape can be traversed and wound up, or a coating liquid-containing reinforcing fiber tape package can be formed by winding in a disk shape, but a winding device (winder) for this purpose is Known materials can be used according to the above.

Winders used for traversing and winding are exemplified in, for example, JP-A-4-119123, JP-A-2008-37650, and JP-A-12122224.
In particular, when winding at a high speed of 100 m/min or more, a bobbin traverse type winder can be used to straighten the yarn path of the coating liquid-containing reinforcing fiber tape. Bending and twisting, and winding disorder on the end surface of the package can be suppressed, which is preferable. A bobbin traverse type winder is exemplified in, for example, Japanese Patent Laid-Open No. 2004-168466.

A reel-shaped winder using a roll with a collar or the like can be used when winding it in a disk shape.

The winding condition can be set with reference to Patent Document 5, JP-A-2017-82209, and the like.

The coating liquid-containing reinforcing fiber tape wound with the coating liquid-containing reinforcing fiber tape is advantageous for large packaging when it is a bobbin shape such as a square end type, and the productivity of the manufacturing process of the coating liquid containing reinforcing fiber tape is improved. Not only this, the time for replacing the coating liquid-containing reinforcing fiber tape package in the subsequent step can be reduced, and the productivity in the subsequent step can be improved, which is preferable. Since the disk-shaped package has a straight yarn path, it is preferable that the coating liquid-impregnated reinforced fiber tape is unlikely to be bent or twisted, or the tape is caught during both winding and unwinding steps.

<Prepreg tape>
When the coating liquid-containing reinforcing fiber tape obtained by the production method of the present invention is used as a prepreg tape, the impregnation rate of the matrix resin is preferably 10% or more. The state of impregnation with the matrix resin can be confirmed by rupturing the collected prepreg tape and visually observing the inside, and more quantitatively, for example, can be evaluated by a peeling method. The impregnation rate of the matrix resin by the peeling method can be measured as follows. That is, the collected prepreg tape is sandwiched between adhesive tapes and peeled off to separate the reinforcing fibers to which the matrix resin is attached and the reinforcing fibers to which the matrix resin is not attached. Then, the ratio of the mass of the reinforcing fibers to which the matrix resin adheres to the mass of the entire reinforcing fiber tape that is put in can be used as the impregnation rate of the matrix resin by the peeling method. In the case of a prepreg tape having a high degree of impregnation, the degree of impregnation can be evaluated by the water absorption rate due to the capillary phenomenon. Specifically, it can be calculated from the mass change when the lower end 5 mm of the prepreg tape is immersed in water for 5 minutes according to the method described in JP-A-2016-510077.

<Multiple lines>
FIG. 14 shows, as an example, an example in which five coating portions are connected in a parallel direction. At this time, the five reinforcing fiber tapes 416 may pass through the five independent reinforcing fiber preheating devices 420 and the coating section 430, so that five coating liquid-containing reinforcing fiber tapes 471 may be obtained. The reinforcing fiber preheating device 420 and the coating unit 430 may be integrated in the parallel direction. In this case, the coating section 430 may be provided with five width regulating mechanisms and five coating section outlet widths independently.

Further, as shown in FIG. 15, the entrance of the wide coating section can be partitioned so that a desired tape width can be obtained and passed through the coating section whose width is adjusted. Further, as shown in FIGS. 16 and 17, it is also possible to dispose the coating portions by shifting them in the horizontal direction or the vertical direction.

<Variations and Applications of the Present Invention>
In the present invention, by using a plurality of coating portions, it is possible to further improve the efficiency of the manufacturing process and increase the functionality thereof.

For example, a plurality of coating parts can be arranged so that a plurality of coating liquid-containing reinforcing fiber tapes are laminated. As an example, FIG. 18 shows an example of a mode in which the coating liquid-containing reinforcing fiber tape is laminated using two coating portions. The two coating liquid-containing reinforcing fiber tapes 471 drawn out from the first coating section 431 and the second coating section 432 are passed through a direction changing roll 445, and are laminated with a release tape or a resin film 443 by a laminating roll 447 therebelow. It is also possible to stack them. It is preferable to position the release tape between the coating liquid-containing reinforcing fiber tape and the direction changing roll, because the prepreg can be prevented from sticking to the nip roll and the running can be stabilized. FIG. 18 exemplifies a device in which a release tape 446 is caused to travel on a circuit on two direction changing rolls 445. The direction change roll may be replaced with a direction change guide that has been subjected to a mold release treatment. In FIG. 18, the high tension take-up device 444 is arranged after the coating liquid-containing reinforcing fiber tape 471 is laminated, but it is of course possible to arrange it before the lamination.

By using such a laminated-type coating liquid-containing reinforcing fiber tape, when the coating liquid-containing reinforcing fiber tape is used as a prepreg tape, the efficiency of the prepreg laminating step can be improved, and for example, a thick FRP can be produced. It is effective when you do. Further, by stacking thin prepreg tapes in multiple layers, it is expected that the toughness and impact resistance of FRP will be improved. By applying this manufacturing method, thin multi-layer prepreg tapes can be efficiently obtained. it can. Further, by stacking different types of prepreg tapes easily, it is possible to easily obtain a hetero-bonded prepreg tape having added functionality. In this case, it is possible to change the type and fineness of the reinforcing fibers, the number of filaments, mechanical properties, fiber surface characteristics and the like. Also, different matrix resins can be used. For example, prepreg tapes having different thicknesses or hetero-bonding prepreg tapes having different mechanical properties can be laminated. In addition, a resin having excellent mechanical properties is applied in the first application section, a resin having excellent tackiness is applied in the second application section, and by laminating these, a prepreg tape capable of achieving both mechanical properties and tackiness can be easily obtained. Can be obtained. On the contrary, it is also possible to dispose a resin having no tackiness on the surface. It is also possible to apply the resin without particles in the first application part and apply the resin containing particles in the second application part.

Further, as another aspect, a plurality of coating portions can be arranged in series in the running direction of the reinforcing fiber tape. FIG. 19 shows an example in which two coating parts are arranged in series. It is preferable to dispose a high tension take-up device 448 between the first applying section 431 and the second applying section 432 from the viewpoint of stabilizing the running of the reinforcing fiber tape 416, but depending on the applying conditions and the taking-off conditions downstream of the process. Can be omitted. Further, when the release tape is positioned between the high-tension take-up device 448 and the coating liquid-containing reinforcing fiber tape pulled out from the first coating section, the coating liquid-containing reinforcing fiber tape is prevented from sticking to the nip roll, and the running is prevented. This is preferable because it can be stabilized. FIG. 19 exemplifies a device in which the high tension take-up device 448 is a nip roll, and the release tape 446 is circuit-run on two rolls.

With such a serial arrangement, the type of coating liquid can be changed in the thickness direction of the coating liquid containing reinforcing fiber tape. Further, even with the same type of coating liquid, it is possible to improve running stability and high-speed running property by changing the application conditions depending on the application part. For example, a prepreg tape capable of providing both mechanical properties and tackiness by applying a matrix resin having excellent mechanical properties in the first application section and a matrix resin having excellent tackiness in the second application section and stacking these Can be easily obtained. On the contrary, it is also possible to dispose a matrix resin having no tackiness on the surface. It is also possible to apply the resin without particles in the first application part and to apply the particle-containing matrix resin in the second application part.

As described above, some modes of arranging a plurality of coating parts are shown, but the number of coating parts is not particularly limited, and various application can be made according to the purpose. Also, it is of course possible to combine these arrangements. Further, various sizes and shapes of the coating part and coating conditions (temperature and the like) can be mixed and used.

As described above, the manufacturing method of the present invention is not only efficient in manufacturing and stable in manufacturing, but also capable of high performance and functionalization of a product, and is a manufacturing method excellent in expandability. In the above, an example of running the reinforcing fiber tape in the vertical direction was shown, but when the reinforcing fiber tape is run in the horizontal direction or the inclined direction and the coating liquid is applied, similar simple additional impregnation, multiple lines are applied. It can take various forms.

As described above, the manufacturing method of the present invention is not only efficient in manufacturing and stable in manufacturing, but also capable of high performance and functionalization of a product, and is a manufacturing method excellent in expandability.

<Coating liquid supply mechanism>
In the present invention, the coating liquid is stored in the coating portion, but it is preferable to replenish the coating liquid appropriately as the coating progresses. The mechanism for supplying the coating liquid to the coating section is not particularly limited, and a known device can be used. It is preferable to continuously supply the coating liquid to the coating unit because the liquid surface above the coating unit is not disturbed and the running of the reinforcing fiber tape can be stabilized. For example, the own weight can be supplied as a driving force from a tank that stores the coating liquid, or can be continuously supplied by using a pump or the like. As the pump, a gear pump, a tube pump, a pressure pump, or the like can be appropriately used depending on the properties of the coating liquid. When the coating liquid is solid at room temperature, it is preferable to provide a melter on the upper part of the reservoir. Also, a continuous extruder or the like can be used. Further, it is preferable to provide a mechanism capable of continuously supplying the coating liquid in accordance with the coating amount so that the liquid surface above the coating portion of the coating liquid is as constant as possible. For this purpose, a mechanism is conceivable in which, for example, the height of the liquid surface or the weight of the coating portion is monitored and fed back to the supply device.

<Online monitoring>
Further, it is preferable to provide a mechanism capable of online monitoring of the coating amount for monitoring the coating amount. The online monitoring method is also not particularly limited, and known methods can be used. For example, a beta ray meter or the like can be used as the device for measuring the thickness. In this case, it is possible to estimate the coating amount by measuring the thickness of the reinforcing fiber tape and the thickness of the coating liquid-containing reinforcing fiber sheet and analyzing the difference. The application amount monitored online is immediately fed back to the application unit and can be used for adjusting the temperature of the application unit and the gap D (see FIG. 2) of the narrowed portion 23. The coating amount monitoring can of course be used as defect monitoring. As the thickness measurement position, for example, referring to FIGS. 12a to 12c, the thickness of the reinforcing fiber sheet 416 is measured in the vicinity of the direction changing roll 419, and the thickness of the prepreg is measured between the application section 430 and the direction changing roll 441. You can It is also preferable to perform online defect monitoring using infrared rays, near infrared rays, a camera (image analysis), or the like.

Hereinafter, specific examples of the present invention will be described in more detail.

FIG. 12a is a schematic view of an example of a prepreg manufacturing process/apparatus using the present invention. Although the plurality of reinforcing fiber bobbins 412 are hung on the creel 411, the reinforcing fiber bundle 414 can be pulled out with a constant tension by a brake mechanism provided to the creel. Here, by pulling out the reinforcing fibers with a constant tension, the width accuracy of the reinforcing fiber tape can be improved. Then, as a tension control device for pulling out the reinforcing fibers, it is preferable to use a creel having an electromagnetic brake mechanism in the spindle portion from the viewpoint of improving the width accuracy and downsizing the entire device. The pulled-out plurality of reinforcing fiber bundles 414 are arranged in order by the reinforcing fiber arrangement device 415, and the reinforcing fiber tape 416 is formed. When one reinforcing fiber bundle yarn is used as the reinforcing fiber tape, the reinforcing fiber arrangement device 414 may not be used. Although only three yarns are drawn in the reinforcing fiber bundle in FIG. 12a, the number of yarns may be one to several hundred yarns in practice. Then, it is conveyed vertically downward through a widening device 417, a smoothing device 418, a direction change roll 419. In FIG. 12a, the reinforcing fiber tape 416 is conveyed linearly between the reinforcing fiber arranging devices 415 to the diversion rolls 419. Note that the widening device 417 and the smoothing device 418 can be appropriately skipped according to the purpose, or the devices can be omitted. Further, the arrangement order of the reinforcing fiber arrangement device 415, the widening device 417, and the smoothing device 418 can be appropriately changed according to the purpose. The reinforcing fiber tape 416 travels vertically downward from the direction changing roll 419, reaches the direction changing roll 441 through the reinforcing fiber preheating device 420 and the coating unit 430. When a plurality of reinforcing fiber tapes are manufactured at the same time, the reinforcing fiber tapes and the coating portions may be in one-to-one correspondence as shown in FIG. 14, or the inside of the wide coating portion may be partitioned as shown in FIG. The reinforcing fiber tape may be passed therethrough. Further, the plurality of coating portions can be arranged in parallel as shown in FIG. 14 or can be arranged in a staggered manner as shown in FIG. Further, it is also possible to arrange them in a staggered pattern as shown in FIG. Further, the application part 430 can adopt any application part shape within the range where the object of the present invention is achieved. For example, the shapes shown in FIG. 2a and FIGS. If necessary, a bush can be provided as shown in FIG. 5a. Further, as shown in FIG. 11, a bar may be provided in the coating section. In FIG. 12 a, the resin film 443 unwound from the resin film supply device 442 is laminated on one side of the coating liquid-containing reinforcing fiber tape 471 on the direction change roll 441, and further, another coating liquid containing reinforcing fiber tape 471 is continuously attached. A resin film can be laminated on one side. Here, the resin film is a laminate with a release tape, and the resin surface is preferably brought into close contact with the surface of the coating liquid containing reinforcing fiber tape. As the release tape, release paper or release film can be used. The resin film and the release tape may be provided as necessary, and in some cases, the device relating to them can be omitted. This can be picked up by the high tension picking device 444. Immediately after coating, a cooling device may be provided as shown in FIG. 5b. In FIG. 12 a, a nip roll is drawn as the high tension take-up device 444. The high tension take-up device can be omitted when the coating liquid has a low viscosity or when the number of lines of the coating liquid-containing reinforcing fiber tape is small. After that, the sheet-like integrated body is passed through an additional impregnation device 450 equipped with a heating plate 451 and a heating nip roll 452, cooled by a cooling device 461, and then taken by a take-up device 462, and after peeling off the upper release tape 446. By winding with a winder 464, it is possible to obtain a sheet-shaped integrated product 472 made of a prepreg tape/release tape as a product. The additional impregnation may be performed if necessary, and in some cases, the additional impregnation machine and the cooling device can be omitted. Since the sheet-shaped integrated product is conveyed in a basic straight line from the direction change roll 441 to the winder 464, wrinkles can be suppressed. The winder may be either traverse winding or disc-shaped winding. When traversing, the winder is disclosed in JP-A-4-119123, JP-2008-37650, and JP-2012-12224A. For example, in order to prevent the coating liquid-containing reinforcing fiber tape from being bent or twisted, or disturbed at the end face of the package, a guide or a traverse mechanism having a design adapted to the tape can be used. When the winding speed is 100 m/min or higher, it is preferable to use a bobbin traverse type winder, but it may be selected in consideration of the layout and cost of the entire manufacturing apparatus. 12A, the drawing of the matrix resin supply device and the online monitoring device is omitted.

FIG. 12a shows an example in which the reinforcing fiber tape is run in the vertical direction and is applied by the application part 430, but by applying the application part 430 in the manner of FIGS. 1b and 2b to 2e as shown in FIG. As in the case of 12a, it is possible to run and apply the reinforcing fiber tape in the horizontal direction or the inclined direction. This is the same in the embodiment shown in FIG. 18 and FIG. 13a and FIGS.

FIG. 12c is a schematic view showing the firing device 411b and subsequent parts in an example of the manufacturing process/apparatus of the reinforcing fiber tape according to the present invention. It is conveyed vertically downward through a surface treatment device 412b, a surface treatment agent drying device 413b, a sizing device 414b, a sizing agent drying device 415b, and a direction change roll 419. In the example of FIG. 12c, the reinforcing fiber tape 416 is conveyed linearly between the devices from the baking device 411b to the direction change roll 419. Note that the widening device 417 and the smoothing device 418 can be appropriately skipped, or the devices can be omitted. Further, the arrangement order of the widening device 417 and the smoothing device 418 can be appropriately changed according to the purpose. Further, depending on the required characteristics, the surface treatment device 412b, the surface treatment agent drying device 413b, the sizing device 414b, and the sizing agent drying device 415b can be omitted. The reinforcing fiber tape 416 travels vertically downward from the direction changing roll 419, reaches the direction changing roll 441 through the reinforcing fiber preheating device 420 and the coating unit 430. When a plurality of reinforcing fiber tapes are supplied at the same time, the reinforcing fiber tapes and the coating portions may be in one-to-one correspondence as shown in FIG. 14, or the inside of the wide coating portion may be partitioned as shown in FIG. The reinforcing fiber tape may be passed therethrough. Further, the plurality of coating portions can be arranged in parallel as shown in FIG. 14 or can be arranged in a staggered manner as shown in FIG. Further, it is also possible to arrange them in a staggered pattern as shown in FIG. Further, the application part 430 can adopt any application part shape within the range where the object of the present invention is achieved. For example, the shapes shown in FIG. 2a and FIGS. If necessary, a bush can be provided as shown in FIG. 5a. Further, as shown in FIG. 11, a bar may be provided in the coating section. In FIG. 12 b, the resin film 443 unwound from the resin film supply device 442 is laminated on one side of the coating liquid-containing reinforcing fiber tape 471 on the direction change roll 441, and subsequently, another coating liquid containing reinforcing fiber tape 471 is formed. A resin film can be laminated on one side. Here, the resin film is a laminate with a release tape, and the resin surface is preferably brought into close contact with the surface of the coating liquid containing reinforcing fiber tape. As the release tape, release paper or release film can be used. The resin film and the release tape may be provided as necessary, and in some cases, the device relating to them can be omitted. This can be picked up by the high tension picking device 444. Immediately after coating, a cooling device may be provided as shown in FIG. 5b. In FIG. 12 b, a nip roll is drawn as the high tension take-up device 444. The high tension take-up device can be omitted when the coating liquid has a low viscosity or when the number of lines of the coating liquid-containing reinforcing fiber tape is small. After that, the sheet-like integrated body is passed through an additional impregnation device 450 equipped with a heating plate 451 and a heating nip roll 452, cooled by a cooling device 461, and then taken by a take-up device 462, after peeling off the upper release tape 446. By winding with a winder 464, it is possible to obtain a sheet-shaped integrated product 472 composed of a prepreg/release sheet as a product. The additional impregnation may be performed if necessary, and in some cases, the additional impregnation machine and the cooling device can be omitted. Since the sheet-shaped integrated product is conveyed in a basic straight line from the direction change roll 441 to the winder 464, wrinkles can be suppressed. The winder may be either a traverse take-up or a disc-like take-up, but at the time of traverse take-up, JP-A-4-119123, JP-A-2008-37650 and JP-A-2012-12224 are available. For example, in order to prevent the coating liquid-containing reinforcing fiber tape from being bent or twisted, or disturbed at the end face of the package, a guide or a traverse mechanism having a design adapted to the tape can be used. Note that the drawing of the matrix resin supply device and the online monitoring device is omitted in FIG. 12b.

FIG. 12c shows an example in which the reinforcing fiber tape is run in the vertical direction in succession to the firing step and is applied by the application section 430. However, as shown in FIG. 12d, the application section 430 is applied in the manner of FIGS. 1b and 2b to 2e. By doing so, the reinforcing fiber tape can be applied while running in the horizontal direction or the inclined direction. This also applies to the embodiment shown in FIG. 18 and FIG. 13b and FIGS.

13a and 13b are schematic views of another example of the manufacturing process/apparatus of the prepreg tape using the present invention. Here, an example using a simple additional impregnation device is shown. In FIGS. 13a and 13b, since the simple additional impregnation device 453 is installed immediately below the coating unit 430, the prepreg tape 471 is guided to the simple additional impregnation device 453 in a high temperature state, which simplifies and reduces the size of the impregnation device. Can be converted. In FIGS. 13a and 13b, the heating nip roll 454 is drawn as an example, but of course, a small heating S-shaped roll may be used depending on the purpose. It is also an advantage that the entire prepreg tape manufacturing apparatus can be made extremely compact by using the simple additional impregnation apparatus. In particular, when the resin film 443 is a resin film containing particles, it is preferable to raise the impregnation degree of the prepreg tape because the particles in the resin film can be arranged on the surface layer of the prepreg tape in the next step.

FIG. 20 is a schematic view of another example of the prepreg tape manufacturing process/apparatus using the present invention. In FIG. 19, an example using 2 rolls-2 sets (total 4 pieces) of a high tension take-up S-shaped roll 449 as a high-tension take-up device and a heating S-shaped roll 455 of “S-lap roll” type as an additional impregnation device is used. Although it is drawn, the number of rolls can of course be increased or decreased depending on the purpose. Further, in FIG. 19, the contact roll 456 for enhancing the impregnation effect is also drawn, but it is of course possible to omit it depending on the purpose.

FIG. 21 is a schematic view of another example of the prepreg manufacturing process/apparatus using the present invention. In this example, an "S-wrap roll" type heated S-shaped roll is also used as a high tension take-up device. There is an advantage that the entire prepreg manufacturing apparatus can be made very compact.

In Examples 1 to 4 below, a reinforced fiber tape using carbon fiber as a reinforced fiber was used, a firing device was attached, and a coating liquid-containing reinforced fiber tape manufacturing method in which a firing step and a coating step were continuously performed was applied. An example of obtaining a liquid-containing reinforcing fiber tape will be described.

<Example 1: Vertical downward running, matrix resin A, with sizing agent>
As the resin-containing reinforcing fiber tape manufacturing apparatus, the apparatus having the configuration shown in FIG. 22b can be used. As the winder, a reel type one wound in a disk shape can be used. 22B, the coating liquid supply device and the online measuring device are not shown. Further, in FIG. 22 b, the direction changing roll 441 is arranged between the winder 464 and the coating unit 430, but the direction changing roll 441 is removed and the coating liquid-containing reinforcing fiber tape 471 coming out of the coating unit 430 is directly fed to the winder 464. You may wind it up.

The coating part can be made of acrylic resin so that the inside can be observed. Further, the running direction of the reinforcing fiber tape in the liquid pool portion is a vertically downward direction, and the liquid pool portion has a two-step taper shape. The first-stage taper has an opening angle of 15 to 20° and a taper length (that is, H). The opening angle of the second step taper can be 10 to 70 mm and 5 to 10°. Further, as the width regulating mechanism, it is possible to provide a plate-shaped bush according to the inner shape of the coating portion as shown in FIG. 5a, and further, by changing the installation position of this plate-shaped bush, L2 can be adjusted appropriately. it can. The gap D in the narrowed portion is set to about 0.2 mm and can be adjusted according to the desired basis weight. Further, in order to prevent the coating liquid from leaking from the outlet of the narrowed portion, the outer side of the bush can be closed on the lower surface of the outlet of the narrowed portion. Further, a measuring instrument for measuring the width of the coating liquid containing reinforcing fiber tape can be installed at the exit of the coating section. For example, an optical width measuring device (LS-7030) manufactured by Keyence Corp. is installed, the width of the coating liquid-containing reinforcing fiber tape is continuously measured on the process, and it is taken into a data logger, and the coating liquid is obtained from the obtained data. The CV value of the width of the contained reinforcing fiber tape can be calculated.

As the reinforcing fiber tape, a carbon fiber tape which has undergone the following steps (2) to (4) can be used. That is, (2) a step of spinning a copolymer composed of acrylonitrile and itaconic acid, and then firing it so that the highest temperature reaches 1000 to 3000° C., (3) a liquid phase using an aqueous solution of ammonium hydrogen carbonate as an electrolytic solution after firing. After the electrolytic oxidation treatment, the liquid phase electrolytic oxidation treatment is performed on the carbon fibers, followed by washing with water and drying in heated air. (4) A sizing agent is added to the carbon fiber tape after the surface oxidation treatment. And the step of performing drying in heated air.

Then, as the matrix resin, an epoxy resin (a mixture of an aromatic amine type epoxy resin and a bisphenol type epoxy resin), a curing agent (dicyandimidide), and a mixture of a curing aid (matrix resin A) are used, and a coating liquid containing reinforcing fiber tape is used. Can be produced. The viscosity of this was measured with ARES-G2 manufactured by TA Instruments at a measurement frequency of 0.5 Hz and a temperature rising rate of 1.5° C./min. 0.6 Pa·s at 40° C. and 3 Pa at 25° C.・S. Using the matrix resin, a coating liquid-containing reinforcing fiber tape can be produced by setting the running speed of the reinforcing fiber tape and the coating liquid-containing reinforcing fiber tape to 1 to 20 m/min.

The evaluation of continuous running property can be performed as follows. That is, the reinforced fiber tape is continuously run for 30 minutes, and there is no fluff clogging or yarn breakage, "Good", and fluff clogging and yarn breakage is "Bad". In addition, in order to evaluate the signs of fluff clogging, the coated portion is disassembled and visually observed after continuous running for 60 minutes and 120 minutes to check the presence or absence of fluff. Anti-fluffing property "Poor" indicates that fluff adheres to the narrowed area after continuous running, the part far from the narrowed area after continuous running (the boundary between the area where the cross-sectional area does not decrease and the area where the cross-sectional area decreases continuously). Those with fluff adhered to (in the vicinity) are referred to as "Fair", and those with no fluff on the liquid contact surface of the wall member after continuous running are referred to as "Good". In addition, the reinforced fiber tape at the boundary between the area where the cross-sectional area does not decrease and the area where the cross-sectional area continuously decreases, is cracked (vertical stripe-like sheet shape) by continuously running for 60 minutes at a running speed of 10 m/min. Measure the time during which the reinforced fiber bundle is running uniformly and that there is no breakage of the reinforcing fiber tape (end of the reinforcing fiber bundle) (end of the reinforcing fiber bundle). "Excellent" means that the time during which the fiber bundle is running uniformly without cracking of the fiber bundle and breakage at the end of the fiber bundle accounts for 90% or more of the total running time, and "Good" when 50% or more and less than 90%. "10% or more and less than 50% is "Fair", and less than 10% is "Poor".

The first step taper of the coating section has an opening angle of 17°, the second step taper has an opening angle of 7°, and the relationship L2-W between the width L2 of the lower end of the width regulating mechanism and the width W of the coating liquid containing reinforcing fiber tape is expressed as follows. When the running property at various running speeds of 10 m/min is evaluated by setting H to 0 mm and H is 30 m/min, there is no fluff/thread clogging (Good) and the fluff prevention property is also Good. When 30 mm>H≧10 mm, there is no fluff/thread clogging (Good), and the fluff prevention property is Fair. When 10 mm>H≧0 mm, the vehicle can run at 20 m/min, but the fluff prevention property is Poor. When the coating part having no portion where the cross-sectional area continuously decreases as shown in FIG. 13 (H=0) is used, the reinforcing fiber sheet is clogged immediately after running at 10 m/min, and continuous running property is obtained. Becomes defective.

Next, when H=70 mm, the relationship L2/W between the width L2 of the lower end of the width regulating mechanism and the width W of the coating liquid containing reinforcing fiber tape was variously evaluated, and 1.1×W<L2 (mm) was obtained. , The crack of the reinforcing fiber tape is Bad, the end of the reinforcing fiber tape is Bad, and the crack of the reinforcing fiber tape is Good, the end of the reinforcing fiber tape is 1.05×W<L2≦1.1×W (mm) With Good Good, 0.8×W≦L2 (mm), the cracks in the reinforcing fiber tape are Excellent, and the end breaks in the reinforcing fiber tape are Excelent.

It can be seen that the smaller the L2/W and the larger the H, the more the stable running property of the coating liquid containing reinforced fiber tape is improved. In addition, the impregnation rate by the peeling method is 50 to 60% in all, and it can be seen that the impregnation is progressing in the coating part. For the impregnation rate by the peeling method, the collected coating liquid containing reinforced fiber tape is sandwiched between adhesive tapes and peeled off to separate the carbon fibers with the matrix resin attached and the carbon fibers without the matrix resin attached It is calculated from the ratio of the mass of the reinforcing fiber to which the matrix resin is attached to the mass of the entire fiber tape.

Further, the uniformity of basis weight in the longitudinal direction of the coating liquid-containing reinforcing fiber tape collected as described above can be evaluated as follows. The coating liquid-containing reinforcing fiber tape is cut out in a lengthwise direction by 100 mm for a total of 1 m, and the mass of the coating liquid containing reinforcing fiber tape and the mass of the carbon fiber are measured. The mass of the carbon fibers is measured as a residue obtained by eluting the resin from the coating liquid-containing reinforcing fiber tape with a solvent. From this, it is understood that when the average value of each value is calculated and the average value is compared with each value, both the carbon fiber and the resin are within the range of plus or minus 2% by mass, and the uniformity of the basis weight in the longitudinal direction is excellent.

Furthermore, when the width accuracy of the coating liquid containing reinforced fiber tape was evaluated, the number of data acquired at a measurement length of about 50 m was about 400, and the CV was about 4%, which is a good width accuracy.

In addition, no scattering of liquid was observed during the coating process during coating, and no process contamination was observed.

<Example 2: Horizontal or inclined traveling, matrix resin A, with sizing agent>
As the resin-containing reinforcing fiber tape manufacturing apparatus, the apparatus having the configuration shown in FIG. 23 can be used. That is, the reinforcing fiber tape is run in the oblique direction in the application part (the path of the reinforcing fiber tape is the same as in FIG. 2c and the dimensions are the same as in Example 1), and the same as in Example 1 except for the applying part. In FIG. 23, the illustration of the coating liquid supply device and the online measuring device is omitted, and the direction changing roll between the coating part and the winder can be removed as in the case of Example 1. Also, the same matrix resin as in Example 1 can be used.

The opening angle of the first step taper of the coating part is 17°, the opening angle of the second step taper is 7°, H=70 mm, L2=W×1 (mm), and the reinforcing fiber tape and coating liquid containing reinforcing fiber tape run When a coating liquid-containing reinforced fiber tape was produced at a speed of 10 m/min and running properties were evaluated, there was no fluff/thread clogging (Good), and fluff prevention was also Good. In addition, the degree of impregnation by the peeling method is about 55%, and the uniformity of the basis weight in the longitudinal direction is good within the range of ±2%.

Furthermore, when the width accuracy of the coating liquid containing reinforced fiber tape was evaluated, the number of data acquired at a measurement length of about 50 m was about 400, and the CV was about 4%, which is a good width accuracy.

In addition, no scattering of liquid was observed during the coating process during coating, and no process contamination was observed.

<Example 3: Vertical downward running, matrix resin A, no sizing agent>
An apparatus having the configuration shown in FIG. 24 can be used as the resin-containing reinforced fiber tape manufacturing apparatus. As the winder, a reel type one wound in a disk shape can be used. Note that, in FIG. 24, the illustration of the coating liquid supply device and the online measuring device is omitted. Further, the direction changing roll between the coating section and the winder can be removed as in Example 1, the coating section is as in Example 1, and the coating liquid can be the matrix resin A as in Example 1. ..

As the reinforcing fiber tape, a reinforcing fiber tape that has undergone the following steps (2) and (3) can be used. That is, (2) a step of spinning a copolymer consisting of acrylonitrile and itaconic acid, and then firing so that the maximum temperature of the heating temperature reaches 1000 to 3000° C., (3) using ammonium hydrogen carbonate aqueous solution as an electrolyte solution after firing. After the liquid-phase electrolytic oxidation treatment, the reinforcing fiber tape subjected to the liquid-phase electrolytic oxidation treatment is subsequently washed with water and dried in heated air.

The opening angle of the first step taper of the coating part is 17°, the opening angle of the second step taper is 7°, H=70 mm, L2=W×1 (mm), and the reinforcing fiber tape and coating liquid containing reinforcing fiber tape run When a coating liquid-containing reinforced fiber tape was produced at a speed of 10 m/min and running properties were evaluated, there was no fluff/thread clogging (Good), and fluff prevention was also Good. The cracks in the reinforced fiber tape were Excellent and the end folds in the reinforced fiber tape were Excellent, but compared with the same conditions of Example 1 (H=70 mm, L2=W×1 (mm)), Example 3 was reinforced fiber There were many cracks and breaks in the tape. The degree of impregnation by the peeling method is about 50%, and the uniformity of the basis weight in the longitudinal direction is good within the range of ±3%.

Furthermore, when the width accuracy of the coating liquid containing reinforced fiber tape was evaluated, the number of data acquired at a measurement length of about 50 m was about 400, and the CV was about 4%, which is a good width accuracy.

In addition, no scattering of liquid was observed during the coating process during coating, and no process contamination was observed.

<Example 4: Vertical downward running, matrix resin B, with sizing agent>
As the resin-containing reinforcing fiber tape manufacturing apparatus, the apparatus having the configuration shown in FIG. 25 can be used. That is, in addition to the device of Example 1, a device configuration mainly including a release tape supplying device, a high tension take-up device, an additional impregnation device, a cooling device, a take-up device, and a winder can be used. Note that, in FIG. 25, the illustration of the coating liquid supply device and the online measuring device is omitted. In addition, the coating part is made of stainless steel, and in order to further heat the matrix resin, a plate heater is attached to the outer periphery of the coating part so that the temperature and viscosity of the matrix resin can be adjusted while measuring the temperature with a thermocouple. You can

As the reinforcing fiber tape, a carbon fiber tape which has undergone the following steps (2) and (3) can be used. That is, (2) a step of spinning a copolymer composed of acrylonitrile and itaconic acid, and then firing it so that the highest temperature reaches 1000 to 3000° C., (3) a liquid phase using an aqueous solution of ammonium hydrogen carbonate as an electrolytic solution after firing. After the electrolytic oxidation treatment, the carbon fiber tape that has been subjected to the liquid-phase electrolytic oxidation treatment is subsequently washed with water and dried in heated air.

Then, as a matrix resin, an epoxy resin (a mixture of an aromatic amine type epoxy resin and a bisphenol type epoxy resin), a curing agent (diaminodiphenyl sulfone), and a mixture of a polyether sulfone (matrix resin B) are used to enhance the coating liquid content. Fiber tape can be made. In addition, when the viscosity of this was measured using ARES-G2 by TA Instruments at a measurement frequency of 0.5 Hz and a heating rate of 1.5° C./min, it was 50 Pa·s at 5° C. and 15 Pa·s at 90° C. 4 Pa·s at 105°C. Using this matrix resin, the matrix resin temperature of the coating part is set to 75 to 105° C., and the running speed of the reinforcing fiber tape and the coating liquid-containing reinforcing fiber tape is set to 1 to 20 m/min to prepare a coating liquid-containing reinforcing fiber tape. it can.

The opening angle of the first step taper of the application part is 17°, the opening angle of the second step taper is 7°, H=70 mm, L2=W×1 (mm), and the matrix resin temperature of the application part is 90° C. When the running speed of the fiber sheet and the reinforcing fiber tape was set to 10 m/min to prepare a coating liquid-containing reinforcing fiber tape and the running property was evaluated, there was no fluff/thread clogging (Good), and the fluff prevention property was also Good. In addition, the degree of impregnation by the peeling method is about 55%, and the uniformity of the basis weight in the longitudinal direction is good within the range of ±2%.

Furthermore, when the width accuracy of the coating liquid containing reinforced fiber tape was evaluated, the number of data acquired at a measurement length of about 50 m was about 400, and the CV was about 4%, which is a good width accuracy.

In addition, no scattering of liquid was observed during the coating process during coating, and no process contamination was observed.

<Prepreg tape manufacturing equipment>
As the prepreg manufacturing apparatus, the apparatus having the configuration shown in FIG. 22a was used. As the creel, one equipped with an electromagnetic brake mechanism was used. As the winder, a reel-type winder was used. Further, no additional impregnation was performed here. 22A, illustration of the coating liquid supply device and the online measuring device is omitted.

<Coating part>
A coating unit of the coating unit 20b type shown in FIG. 6 was used. In the coating portion, a stainless steel block was used for the wall surface member forming the liquid pool portion and the narrowed portion, and a stainless steel plate was used for the side plate member. Further, in order to heat the matrix resin, a plate heater was attached to the outer periphery of the wall member and the side plate member, and the temperature and viscosity of the matrix resin were adjusted while measuring the temperature with a thermocouple. The running direction of the reinforcing fiber sheet was downward in the vertical direction, and the taper of the liquid pool was at an opening angle of 30°. Further, as the width regulating mechanism, a plate-shaped bushing according to the internal shape of the coating portion as shown in FIG. 5A is provided, and further, the installation position of this plate-shaped bushing can be freely changed so that L2 can be adjusted appropriately. L2 was set to 10 mm. The gap D in the narrowed portion was 0.2 mm. Further, in order to prevent the coating liquid from leaking from the outlet of the narrowed portion, the outer side of the bush was closed at the lower surface of the outlet of the narrowed portion.

<Reinforcing fiber tape>
The following were used as the reinforcing fibers.
Reinforcing fiber 1: Carbon fiber (manufactured by Toray, "Torayca (registered trademark)" T800S (24K))
Reinforcing fiber 2: Carbon fiber ("Torayca (registered trademark)" T720S (36K) manufactured by Toray)
Then, one yarn of the above-mentioned reinforcing fiber was used as a reinforcing fiber tape.

<Matrix resin>
Matrix resin A:
A mixture of an epoxy resin (a mixture of an aromatic amine type epoxy resin and a bisphenol type epoxy resin), a curing agent and a polyether sulfone was used.

The viscosity of this was measured using ARES-G2 manufactured by TA Instruments at a measurement frequency of 0.5 Hz and a temperature rising rate of 1.5° C./min, and was 15 Pa·s at 90° C. and 200 Pa·s at 60° C. It was

Matrix resin B:
It is a mixture of an epoxy resin (a mixture of an aromatic amine type epoxy resin and a bisphenol type epoxy resin), a curing agent and a curing aid. The viscosity of this was measured by using ARES-G2 manufactured by TA Instruments at a measurement frequency of 0.5 Hz and a temperature rising rate of 1.5° C./minute, and was 0.6 Pa·s at 40° C. and 3 Pa·s at 25° C. Met.

<Evaluation of continuous running performance>
In order to evaluate the continuous running property of the reinforcing fiber sheet in the coating portion, the running was continued for 30 minutes, and the one without fluffing or thread breakage was "Good", and the one with fluffy thread breakage was "Bad".

In addition, in order to evaluate the signs of fluff clogging, the coated portion was disassembled after 60 minutes and 120 minutes of continuous running, and the liquid contact surface of the wall surface member was visually observed to check the presence or absence of fluff. What has fluff adhered in the vicinity of the narrowed portion after continuous running is "Poor" anti-fluff property, and what has fluff adhered to the portion far from the narrowed portion 23 (near the upper part of the liquid pool 22) after continuous running. The fluff prevention property "Fair" and the fluff prevention property "Good" was evaluated when the fluff was not adhered to the liquid contact surface of the wall surface member 21 after continuous running.

Also, by continuously running for 60 minutes at a running speed of 20 m/min, the reinforcing fiber sheet directly above the liquid pool portion has a fiber bundle crack (a portion where the sheet-like carbon fiber bundle is split in the form of vertical stripes) or an end portion of the fiber bundle is broken. The time during which there was no (the portion where the carbon fiber bundles overlap) was running uniformly was measured. "Excellent" means that the time during which the fiber bundle is running uniformly without cracking of the fiber bundle and breakage at the end of the fiber bundle accounts for 90% or more of the total running time, and "Good" when 50% or more and less than 90%. "10% or more and less than 50% was designated as "Fair" and less than 10% was designated as "Poor".

<Evaluation of degree of impregnation>
The collected prepreg tape was sandwiched between adhesive tapes and peeled off to separate the reinforcing fibers to which the matrix resin adheres and the reinforcing fibers to which the matrix resin does not adhere. Then, the ratio of the mass of the reinforcing fibers to which the matrix resin adheres to the mass of the entire reinforcing fiber tape that was added was defined as the impregnation rate of the matrix resin by the peeling method.

<Evaluation of width accuracy of prepreg tape>
An optical width measuring device (LS-7030) manufactured by Keyence Corporation was installed immediately below the coating part, the prepreg tape width was continuously measured on the process, and it was taken into a data logger. The CV value of the prepreg tape width was calculated from the obtained data.

[Examples 1 to 3 and Reference Example 1 ]
CF1 was used as the reinforcing fiber, the matrix resin A was used as the coating liquid, the matrix resin temperature of the coating part was 90° C., and the running speed of the reinforcing fiber tape was 20 m/min to prepare a prepreg tape. Relationship between the width L2 of the lower end of the width regulation mechanism and the width W of the prepreg tape L2-W and the running stability of the prepreg tape at the coating part when the height H at which the cross-sectional area of the coating part continuously decreases are changed. The evaluation results of are shown in Table 1.

From this, it is understood that the running stability and the fluff prevention property are better as H is larger and L2-W is smaller.

Further, when the width accuracy of the prepreg tape was evaluated, as shown in Table 1, in Examples 1 to 3 , CV=5% or less, which was a good width accuracy. The number of measured tape widths when obtaining the CV value will be described. The number of data acquisitions was 427/57.2 m.

In addition, the impregnation rate was 50% or more in all of the examples, and it was confirmed that the impregnation is progressing. The resin content of the entire prepreg tape was about 25% by mass.

[Comparative Example 1]
As a coating part, a part without a portion where the cross-sectional area shown in FIG. 10 continuously decreases (H=0) was used, and an attempt was made to prepare a prepreg in the same manner as in Example 1 under the conditions shown in Table 1. Immediately after the start of running in minutes, the reinforcing fiber sheet was clogged and the continuous running property was poor.

[Comparative example 2]
The prepreg tape was manufactured in the same manner as in Example 5 except that the relationship L2-W between the width L2 of the lower end of the width regulation mechanism and the width W of the prepreg tape was set to 2 mm. When the width accuracy of the prepreg tape was evaluated, it was CV=6%, and the width accuracy did not reach that of Examples 1 to 4, and the tape width varied greatly. When the prepreg tapes were laminated, the tapes overlap with each other and there is a possibility that local thickness defects will occur. The data acquisition number was 427/57.2 m.

[ Reference Example 2 ]
As the prepreg manufacturing apparatus, the apparatus having the configuration shown in FIG. 22c, in which the cooling apparatus 433 was further provided in the apparatus having the configuration shown in FIG. 22a, was used. CF1 was used as the reinforcing fiber, the matrix resin A was used as the coating liquid, the matrix resin temperature of the coating part was 90° C., and the running speed of the reinforcing fiber tape was 20 m/min to prepare a prepreg tape. The temperature of the coating liquid containing reinforcing fiber tape after the cooling device 433 was 60°C. The relation L2-W between the width L2 at the lower end of the width regulating mechanism and the width W of the prepreg tape and the height H at which the cross-sectional area of the coating portion continuously decreases were the same as those in Reference Example 1 . The results are shown in Table 2. When the width accuracy of the prepreg tape was evaluated, it was CV=4%, and the width accuracy was improved as compared with Reference Example 1 by using the cooling device.

[Example 6]
CF2 was used as the reinforcing fiber, matrix resin B was used as the coating liquid, the matrix resin temperature of the coating portion was 40° C., and the running speed of the reinforcing fiber tape was 125 m/min to prepare a prepreg tape. The relation L2-W between the width L2 of the lower end of the width regulating mechanism and the width W of the prepreg tape was zero, and the height H at which the cross-sectional area of the coating portion continuously decreased was 50 mm.

At this time, stable running was possible at 125 m/min for 30 minutes or more without fluffing or thread breakage. Also, no cracks or breaks were observed at the tape edges.

Next, when the width accuracy of the prepreg tape was evaluated, the CV was 2%, which was an excellent width accuracy. The number of data acquired was 136/114 m. Further, when the obtained prepreg tape was torn by hand to check the inside, it was confirmed that the reinforcing fiber inside was wet with the coating liquid (matrix resin B) and the impregnation degree was also good. The resin content of the entire prepreg tape was about 27% by mass.

Further, when the prepreg tape was unwound from the obtained prepreg tape winding package, almost no tackiness was felt on the surface of the prepreg tape, and the prepreg tape was not used in combination with a support such as a release tape. The rolling property was good.

The coating liquid-containing reinforcing fiber tape obtained by the production method of the present invention is used as an FRP typified by CFRP for structural materials and interior materials for aviation/space applications, automobiles/trains/ships, pressure vessels, industrial material applications, and sports. It can be widely applied to materials, medical devices, housings, civil engineering and construction, etc.

DESCRIPTION OF SYMBOLS 1 reinforced fiber 1a reinforced fiber tape 1b coating liquid containing reinforced fiber tape 2 coating liquid 3 release tape or resin film 11 creel 11a baking device 12 arranging device 13, 14 conveying roll 15 winding device 16, 16a, 16b supply device 20 coating Section 20b Coating section 20c according to another embodiment Coating section 20d according to another embodiment Coating section 20e according to another embodiment Coating sections 21a and 21b according to another embodiment Wall surface members 21c and 21d Wall surface members 21e and 21f with different shapes Wall member 21g, 21h of another shape Wall member 21i, 21j of another shape Wall member 22 of another shape Liquid pool part 22a Area 22b of the liquid pool where the cross-sectional area continuously decreases Disconnection of the liquid pool part Region 22c where the area is not reduced Region 23 where the cross-sectional area is reduced intermittently in the liquid pool 23 Constricted portions 24a, 24b Side plate member 25 Outlet 26 Gap 27, 27a, 27b Width regulation mechanism 30 Coating parts 31a, 31b of Comparative Example 1 Wall Member 32 of Comparative Example 1 Liquid Pool 33 of Comparative Example 1 Regions 35a, 35b, 35c of the liquid pool of Comparative Example 1 in which the cross-sectional area decreases intermittently 56 degassing mechanism 60 opening 61 direction changing member 62 Cooling device 100 Coating device B Depth of the liquid pool 22 C Height to the upper liquid surface of the liquid pool 22 D Gap of the narrowed portion G Width regulation position H The cross-sectional area of the liquid pool 22 is continuous Reduced vertical height L Widths R, Ra, Rb of liquid pool 22 Vortex flow T Circulating flow U Width W of constriction 23 W Width of coating liquid containing reinforced fiber tape measured directly below constriction X Horizontal direction Y Orthogonal direction to X and Z Z Running direction of the reinforcing fiber tape 1a (vertical direction downward)
θ Opening angle of taper part 411 Creel 411b Firing device 412 Reinforcing fiber bobbin 412b Surface treating device 413 Direction change guide 413b Surface treating agent drying device 414 Reinforcing fiber bundle 414b Sizing device 415 Reinforcing fiber arranging device 415b Sizing agent drying device 416 Reinforcement Fiber tape 417 Widening device 418 Smoothing device 419 Direction changing roll 420 Reinforcing fiber preheating device 430 Applying part 431 First applying part 432 Second applying part 433 Cooling device 441 Direction changing roll 442 Release tape or resin film supplying device 443 Release tape or resin film 444 High-tension take-up device 445 Direction change roll 446 Release tape 447 Laminating roll 448 High-tension take-up device 449 High-tension take-up S-shaped roll 450 Additional impregnation device 451 Hot plate 452 Heating nip roll 453 Simple add-on Impregnation device 454 Heating nip roll 455 Heating S-shaped roll 456 Contact roll 461 Cooling device 462 Take-up device 463 Release tape (upper) Winding device 464 Winder 471 Prepreg (Reinforced fiber tape containing coating liquid)
472 prepreg/release tape (integral sheet)

Claims (12)

A method for producing a coating liquid-containing reinforcing fiber tape, which is obtained by passing a reinforcing fiber tape having a tape width of 3 to 30 mm and applying the coating liquid to the reinforcing fiber tape inside the coating portion in which the coating liquid is stored. hand,
The coating section includes a liquid pool section and a narrowed section that are in communication with each other,
The liquid pool portion has a portion whose cross-sectional area continuously decreases along the running direction of the reinforcing fiber tape,
The narrowed portion has a slit-shaped cross section, and has a cross-sectional area smaller than the upper surface of the liquid pool portion,
The width L (mm) of the lower portion of the liquid pool portion in the tape width direction of the reinforcing fiber tape regulated by the side plate member forming the liquid pool portion and the width W (mm) of the tape-shaped reinforcing fiber immediately below the narrowed portion are , L≦1.1×W is satisfied,
The width variation coefficient (CV) of the coating liquid containing reinforcing fiber tape pulled out from the narrowed portion is 5% or less,
A method for producing a coating liquid-containing reinforcing fiber tape. A method for producing a coating liquid-containing reinforcing fiber tape, which is obtained by passing a reinforcing fiber tape having a tape width of 3 to 30 mm and applying the coating liquid to the reinforcing fiber tape inside the coating portion in which the coating liquid is stored. hand,
The coating section includes a liquid pool section and a narrowed section that are in communication with each other,
The liquid pool portion has a portion whose cross-sectional area continuously decreases along the running direction of the reinforcing fiber tape,
The narrowed portion has a slit-shaped cross section, and has a cross-sectional area smaller than the upper surface of the liquid pool portion,
The width W of the reinforcing fiber tape immediately below the narrowed portion is provided in the liquid pool portion with a width regulating mechanism that is a plate-shaped bush along the inner shape of the coating portion from the middle portion to the lower portion for regulating the width of the reinforcing fiber tape. (Mm) and the width L2 (mm) regulated by the width regulation mechanism at the lower end of the width regulation mechanism satisfy L2≦1.1×W (mm),
The width variation coefficient (CV) of the coating liquid containing reinforcing fiber tape pulled out from the narrowed portion is 5% or less,
A method for producing a coating liquid-containing reinforcing fiber tape . The method according to claim 1 or 2 , which has a firing step in which the highest temperature reaches 1000 to 3000°C, and at least the steps from the firing step to the step of applying the coating liquid to the reinforcing fiber tape are continuously performed. Of the coating liquid-containing reinforcing fiber tape of. The length of the portion where the cross-sectional area of the liquid pool portion continuously decreases is 10 mm or more,
The manufacturing method of the coating liquid containing reinforced fiber tape according to any one of claims 1 to 3 . The method for producing a coating liquid-containing reinforcing fiber tape according to any one of claims 1 to 4 , wherein the coating liquid is applied to the reinforcing fiber tape by passing the reinforcing fiber tape substantially vertically downward in the coating section. .. The coating liquid-containing reinforcing fiber tape according to any one of claims 1 to 4 , wherein the coating liquid is applied to the reinforcing fiber tape by allowing the reinforcing fiber tape to pass in a substantially horizontal direction or an inclined direction in the coating section. Production method. The viscosity of the coating liquid is not more than 2 Pa · s, coating liquid containing reinforcing fibers tape manufacturing method according to any one of claims 1-6. The method for producing a coating liquid-containing reinforcing fiber tape according to any one of claims 1 to 7 , wherein the coating liquid containing reinforcing fiber tape pulled out from the narrowed portion is subjected to additional impregnation. 9. The coating liquid containing according to claim 1, wherein the reinforcing fiber tape is introduced into the inside of the coating part after being pulled out by using a creel equipped with an electromagnetic brake mechanism. Manufacturing method of reinforcing fiber tape. A method for producing a coating liquid-containing reinforcing fiber tape package, which comprises traversing and winding the coating liquid-containing reinforcing fiber tape according to any one of claims 1 to 9 . The coating liquid containing the reinforcing fiber tape of any one of claims 1 to 9, wound in the shape of a disc, the manufacturing method of the coating liquid containing reinforcing fibers tape package. The method for producing a coating liquid-containing reinforcing fiber tape package according to claim 10 , wherein only the coating liquid-containing reinforcing fiber tape is wound.