WO2020040151A1

WO2020040151A1 - Method for producing coating-liquid-containing reinforcing fiber tape and coating-liquid-containing reinforcing fiber tape package

Info

Publication number: WO2020040151A1
Application number: PCT/JP2019/032493
Authority: WO
Inventors: 河野祥和; 越智隆志; 青木惇一; 西野聡
Original assignee: 東レ株式会社
Priority date: 2018-08-22
Filing date: 2019-08-20
Publication date: 2020-02-27
Also published as: JP6708311B1; JPWO2020040151A1

Abstract

The present invention addresses the problem of providing a method for producing a coating-liquid-containing reinforcing fiber tape in which fluff generation is suppressed and continuous production without clogging by fluff is made possible, and furthermore in which it is possible to impregnate the reinforcing fiber tape with the coating liquid efficiently and to increase the production speed. The main object of the present invention is a method for producing a coating-liquid-containing reinforcing fiber tape in which a reinforcing fiber tape having a tape width of 3-30 mm is passed through the inside of an application part in which the coating liquid is stored to apply the coating liquid to the reinforcing fiber tape, wherein the application part comprises a liquid reservoir part and a narrowed part that are in communication with each other, the liquid reservoir part has a portion in which the cross-sectional area decreases continuously along the running direction of the reinforcing fiber tape, the narrowed part has a slit-shaped cross-section and has a cross-sectional area smaller than that of an upper surface of the liquid reservoir part, and the width coefficient of variation (CV) of the coating-liquid-containing reinforcing fiber tape drawn out from the narrowed part is 5% or less.

Description

Coating liquid-containing reinforcing fiber tape and method for producing coating liquid-containing reinforcing fiber tape package

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

Fiber reinforced composite material (FRP), which is a matrix resin containing thermoplastic resin and thermosetting resin reinforced with reinforcing fibers, is a material for aviation and space, automotive material, industrial material, pressure vessel, building material, housing, medical equipment. It is used in various fields such as applications and sports. Particularly when high mechanical properties and lightness are required, carbon fiber reinforced composite materials (CFRP) are widely and suitably used. On the other hand, when cost is prioritized over mechanical properties and light weight, a glass fiber reinforced composite material (GFRP) may be used. In the 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, is thermoset to produce a member made of FRP. In the above-mentioned applications, there are many planar objects and those obtained by bending the same, and the two-dimensional sheet-like material is more often used as an intermediate substrate of FRP than a one-dimensional strand or roving-like material when producing a member. It is widely used from the viewpoint of lamination efficiency and moldability.

最近 In recent years, in order to improve the production efficiency of members made of FRP, mechanization and automation of lamination of sheet-like intermediate substrates have been promoted, and narrow-width tape-like intermediate substrates are preferably used here. The narrow tape-shaped intermediate substrate can be obtained by slicing a wide sheet-shaped intermediate substrate at a desired width, or by impregnating a narrow reinforcing fiber sheet directly with a matrix resin.

(4) A method for producing a carbon fiber UD substrate will be briefly described. First, after firing a plurality of yarns, a surface treatment and a sizing agent are applied, and the yarns are wound around a bobbin as a carbon fiber tape. After that, the hot melt method, which is one of the prepreg manufacturing methods, melts the matrix resin, coats it on release paper, and creates a laminated structure sandwiched between the upper and lower surfaces of the reinforcing fiber sheet. The matrix resin is impregnated inside 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, a method of producing a prepreg in which a matrix resin is impregnated into carbon fibers immediately after a firing step in a carbon fiber production process has been proposed (Patent Document 1). When this method is used, the steps of applying a sizing agent, winding a bobbin, and unwinding carbon fibers at the time of prepreg manufacture can be simplified, and the number of steps can be reduced.

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

提案 There has been a proposal for improving the efficiency of impregnation, for example, as in Patent Document 2. In this method, a glass fiber is melt-spun and then bundled into a strand or roving to pass through a liquid reservoir having a conical flow path filled with a thermoplastic resin.

On the other hand, Patent Document 3 discloses a method for simultaneously forming a coating film on both surfaces of a sheet material. In this method, a sheet material is passed through a web guide in order to prevent fluctuation of the sheet material at the time of forming a coating film. After that, coating is performed with a pipe type doctor.

As a method for producing a strip-shaped prepreg using a thermoplastic resin, a strip-type reinforcing fiber bundle is conveyed in a horizontal direction (horizontal direction), passed through a die, and a thermoplastic resin is applied to and impregnated into the strip-shaped reinforcing fiber bundle. Patent document 4) is known. In Patent Document 3, a plurality of band-shaped reinforcing fiber bundles are separately introduced into a die filled with a molten thermoplastic resin, and are opened, impregnated, and laminated by a fixed guide (for example, a squeeze bar). It is described that the sheet-shaped prepreg is pulled out from a die.

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

Further, among prepregs, as a method for producing a tow prepreg in which a matrix resin is applied to one yarn of a reinforcing fiber bundle, a matrix resin can be applied by contacting a reinforcing fiber bundle with a kiss roll as described in Patent Document 6. Is being done.

改善 Improvement of the coating method not only in the prepreg manufacturing process but also in the carbon fiber manufacturing process has been proposed. For example, in Patent Literature 7, a sizing agent is applied by roll coating, and air is applied to the applied carbon fiber to adjust the amount of application.

JP 2003-268137 A International Publication WO2001 / 028951 pamphlet JP-A-10-337516 International Publication WO2012 / 002417 pamphlet JP-A-1-178412 JP 2012-184279 A 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, there is a possibility that the width of the tape and the basis weight of the resin may fluctuate.

では The method of Patent Document 2 can only produce strands or rovings, and cannot be applied to the production of sheet prepregs that are the subject of the present invention. Further, in Patent Literature 1, in order to improve the impregnation efficiency, a fluid of a thermoplastic resin is applied to the strand or the side surface of the roving-like reinforcing fiber bundle to generate turbulent flow positively in the conical flow path. This is thought to be intended to partially disturb the arrangement of the reinforcing fiber bundle and allow the matrix resin to flow in.However, when this concept is applied to the reinforcing fiber sheet, the reinforcing fiber sheet is deformed, and the quality of the prepreg is reduced. It is thought that not only does the FRP decrease, but also the mechanical properties of the FRP decrease.

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

では In addition, in the method of Patent Document 4, fluff is likely to stay in the liquid pool during continuous production, and fluff is likely to be clogged in the withdrawn portion. In particular, when the band-shaped reinforcing fiber bundle is continuously run at a high speed, the frequency of clogging of the fluff is extremely increased, so that production can be performed only at a very low speed, and there is a problem that productivity is not improved. Further, in the case of the horizontal drawing method, it is necessary to seal the die portion to prevent liquid leakage, and it is not sufficient to collect fluff during continuous production. Furthermore, in the horizontal drawing method, when the matrix resin is impregnated inside the reinforcing fiber sheet, the air bubbles remaining inside the band-shaped reinforcing fiber bundle are buoyant to a direction orthogonal to the orientation direction of the reinforcing fiber bundle (band-shaped reinforcing fiber). Since the gas is discharged in the direction of the thickness of the fiber bundle (the thickness direction of the fiber bundle), the discharge of the bubbles proceeds as if the impregnated matrix resin is pushed away. Therefore, there is a problem that impregnation efficiency is poor because the movement of bubbles is inhibited by the liquid and the impregnation of the matrix resin is also inhibited by the bubbles. Further, it has been proposed to exhaust air bubbles from the vent, but only in the vicinity of the die outlet, and the effect is considered to be limited.

Further, in the method described in Patent Document 5, a nozzle portion not filled with resin is provided on the upper portion of the manifold, and the nozzle can be optimized with a strand or a roving-like material. It is difficult to cope with the shape, and when the reinforcing fiber sheet passes therethrough, fluff is generated, and when it is brought into the manifold, it is considered that it is likely to be clogged with a die.

In the method using a kiss roll described in Patent Document 6, there is not much problem when the production speed is as low as described in the document. However, when the production speed is further increased and the matrix resin has a low viscosity, resin scattering occurs. There is a possibility that the area around the apparatus becomes dirty, the process stability is reduced, and the production efficiency is reduced due to the stoppage of the apparatus for cleaning. Furthermore, the width variation of the reinforcing fiber bundle on the kiss roll is large in nature, especially when the production speed is increased, and the fluctuation of the applied amount of the matrix resin and the width of the tow prepreg may become large. Conceivable.

Furthermore, in the coating method described in Patent Document 7, when the coating amount is adjusted by air, the coating liquid is scattered to the surroundings, thereby contaminating the process, and the device is stopped for cleaning, thereby lowering the manufacturing efficiency. Problems can occur. In addition, when applied to the application of a matrix resin, it is conceivable that the applied amount of the matrix resin and the fluctuation of the width of the tow prepreg become large.

Thus, 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 applying method capable of improving tape width accuracy has not been established. Was.

An object of the present invention is to provide 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. It is an object of the present invention to provide a method for producing a coating liquid-containing reinforcing fiber tape that can increase the speed.

The method for producing a coating liquid-containing reinforcing fiber tape according to the present invention that solves the above-mentioned problems is characterized in that the coating liquid is reinforced by passing a reinforcing fiber tape having a tape width of 3 to 30 mm into an application section in which the coating liquid is stored. A method for producing a coating liquid-containing reinforcing fiber tape to be applied to a fiber tape, wherein the application section includes a liquid pool section and a narrowed section which are communicated with each other, and the liquid pool section is cut along a running direction of the reinforcing fiber tape. The narrow portion has a slit-shaped cross section, and has a cross-sectional area smaller than the upper surface of the liquid reservoir portion, and the coating liquid-containing reinforcing fiber tape pulled out from the narrow portion has an area having a continuously decreasing area. Is a method for producing a coating-solution-containing reinforcing fiber tape having a width variation coefficient (CV) of 5% or less.

The method for manufacturing a coating liquid-containing reinforcing fiber tape package of the present invention is a method for manufacturing a coating liquid-containing reinforcing fiber tape package in which the coating liquid-containing reinforcing fiber tape is traversed or wound into a disk 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 are improved. Further, the reinforcing fiber tape can be run continuously, thereby improving the productivity and obtaining a high-quality coating liquid-containing reinforcing fiber tape free from breakage or the like.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross-sectional view which shows the manufacturing method of the coating liquid containing reinforcing fiber tape and coating device which concern on one Embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross-sectional view which shows the manufacturing method of the coating liquid containing reinforcing fiber tape and coating device which concern on one Embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross-sectional view which shows the manufacturing method of the coating liquid containing reinforcing fiber tape and coating device which concern on one Embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross-sectional view which shows the manufacturing method of the coating liquid containing reinforcing fiber tape and coating device which concern on one Embodiment of this invention. FIG. 2 is an enlarged detailed cross-sectional view of a portion of a coating unit 20 in FIG. 1A. FIG. 4 is a schematic cross-sectional view showing a method for producing a coating liquid-containing reinforcing fiber tape and a coating apparatus according to another embodiment of the present invention. FIG. 4 is a schematic cross-sectional view showing a method for producing a coating liquid-containing reinforcing fiber tape and a coating apparatus according to another embodiment of the present invention. FIG. 4 is a schematic cross-sectional view showing a method for producing a coating liquid-containing reinforcing fiber tape and a coating apparatus according to another embodiment of the present invention. FIG. 4 is a schematic cross-sectional view showing a method for producing a coating liquid-containing reinforcing fiber tape and a coating apparatus according to another embodiment of the present invention. FIG. 3 is a bottom view of the application unit 20 in FIG. 2 as viewed from a direction A in FIG. 2. FIG. 3 is a cross-sectional view illustrating a structure inside the coating unit when the coating unit 20 in FIG. 2 is viewed from a direction B in FIG. 2. It is sectional drawing showing the flow of the coating liquid 2 in the clearance gap 26 in FIG. 4a. It is a figure showing an example of installation of a width regulation mechanism. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross-sectional view which shows the manufacturing method of the coating liquid containing reinforced fiber tape and the coating apparatus which concerns on one Embodiment of this invention provided with the cooling device 61. FIG. 4 is a detailed cross-sectional view of a coating unit 20b according to another embodiment different from FIG. 2. FIG. 7 is a detailed cross-sectional view of a coating unit 20c according to another embodiment different from FIG. 6. FIG. 7 is a detailed cross-sectional view of a coating unit 20d according to another embodiment different from FIG. 6. FIG. 7 is a detailed cross-sectional view of a coating unit 20e according to another embodiment different from FIG. FIG. 4 is a detailed cross-sectional view of a coating unit 30 according to an embodiment different from the present invention. It is a figure showing the mode provided with the bar in the liquid pool part which is an example of an embodiment of the present invention. It is the schematic which shows the example of the prepreg tape manufacturing process and apparatus using this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which shows the example of the manufacturing process and apparatus of a coating liquid containing reinforced fiber tape using this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which shows the example of the manufacturing process and apparatus of a coating liquid containing reinforced fiber tape using this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which shows the example of the manufacturing process and apparatus of a coating liquid containing reinforced fiber tape using this invention. It is the schematic of an example of another prepreg tape manufacturing process and apparatus using this invention. It is the schematic of an example of another manufacturing process and apparatus of a coating liquid containing reinforcing fiber tape using this invention. FIG. 3 is a diagram illustrating an example of a multi-line mode according to an embodiment of the present invention. FIG. 3 is a diagram illustrating an example of a multi-line mode according to an embodiment of the present invention. FIG. 3 is a diagram illustrating an example of a multi-line mode according to an embodiment of the present invention. FIG. 3 is a diagram illustrating an example of a multi-line mode according to an embodiment of the present invention. It is a figure showing the example of the mode of laminating a plurality of prepreg tapes concerning one embodiment of the present invention. It is a figure showing the example of the mode provided with a plurality of application parts concerning one embodiment of the present invention. It is the schematic of an example of another prepreg tape manufacturing process and apparatus using this invention. It is the schematic of an example of another prepreg tape manufacturing process and apparatus using this invention. It is the schematic of an example of another prepreg tape manufacturing process and apparatus using this invention. It is the schematic of an example of another manufacturing process and apparatus of a coating liquid containing reinforcing fiber tape using this invention. It is the schematic of an example of another manufacturing process and apparatus of a coating liquid containing reinforcing fiber tape using this invention. It is the schematic of an example of another manufacturing process and apparatus of a coating liquid containing reinforcing fiber tape using this invention. It is the schematic of an example of another manufacturing process and apparatus of a coating liquid containing reinforcing fiber tape using this invention. It is the schematic of an example of another manufacturing process and apparatus of a coating liquid containing reinforcing fiber tape using this invention.

望ましい Preferred embodiments of the present invention will be described with reference to the drawings. Note 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 the method for producing a coating liquid-containing reinforcing fiber tape>
First, an outline of a method for producing a 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 transport mechanisms for transporting the reinforcing fiber tape 1a substantially vertically downward Z, and stores the coating liquid 2 therein. Coating section 20 is provided. In addition, before and after the coating apparatus 100, a creel 11 for unwinding the reinforcing fibers 1 and a reinforcing fiber tape 1a in which the unwound reinforcing fibers 1 are arranged in one direction (in FIG. 1, arranged in the depth direction of the paper) are obtained. An arrangement device 12 and a winding device 15 for the coating liquid-containing reinforcing fiber tape 1b 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 refers to a coating liquid applied to a reinforcing fiber tape, and the coating liquid may be present on the surface, or a part or all of the coating liquid. May be impregnated inside the reinforcing fiber tape. Although FIG. 1A shows a mechanism in which the coating apparatus travels in the vertical direction, it may travel in a horizontal direction as shown in FIG. 1B, as described later.

{Circle around (1)} FIG. 1c is a schematic view of a method for producing a coating liquid-containing reinforcing fiber tape having a baking 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 maximum 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 fiber is baked and then reinforced into a tape to form a reinforcing fiber tape, and the carbon fiber is applied until the coating liquid is applied to the reinforcing fiber tape. 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 section, and the linear velocity when the coating liquid-containing reinforcing fiber tape is wound up are basically equal. Here, before the coating liquid is applied, the coating liquid may be subjected to a surface treatment step, a sizing step, a drying step, a carbon fiber tape smoothing device and a widening device, which will be described later. The carbon fibers exit the firing step 11 and are guided to the coating apparatus 100. In the coating apparatus 100, as in FIG. 1A, transport rolls 13 and 14 for guiding the reinforcing fiber tape 1a made of carbon fiber to the inside of the coating apparatus 100 are provided between the transport rolls 13 and 14, and the coating liquid is provided. 2 is provided with an application section 20 in which 2 is stored. 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, a supply device 16 for supplying the release tape 3 is provided as needed, as in FIG. 1A. Although FIG. 1c shows a mechanism in which the coating device travels in the vertical direction, the reinforcing fiber tape may travel in the horizontal direction as shown in FIG. 1d, as described later. When the fired carbon fibers are arranged in a tape shape, if the running paths of the carbon fibers are arranged neatly at the exit of the firing step, it can be obtained without using any special device. 1d does not show a device for preparing the fired carbon fiber into a tape shape. Of course, in order to arrange the carbon fibers into a tape shape, a mechanism for adjusting the arrangement of the fibers, such as a guide or a roll, 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 fibers from the viewpoint of the mechanical properties and light weight of the FRP.

As a reinforcing fiber tape, a unidirectional material (UD base material) in which a plurality of reinforcing fibers are arranged on a surface in one direction, a reinforcing fiber in which reinforcing fibers are arranged in a multiaxial manner, or a tape which is randomly arranged and formed into a tape. Fabric.

The method for forming the UD base material can be a known method, and is not particularly limited. 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. Forming is preferable from the viewpoint of process efficiency and uniform array. For example, in carbon fiber, a tape-shaped reinforcing fiber bundle "tow" is wound around a bobbin, and a tape-shaped reinforcing fiber bundle drawn from this is used as one yarn, or these are arranged in a plurality of yarns. Thus, a reinforcing fiber tape can be obtained. It also has a reinforcing fiber arrangement mechanism for neatly arranging reinforcing fiber bundles drawn from creeled bobbins, eliminating undesirable overlapping and folding of reinforcing fiber bundles in reinforcing fiber tape, and gaps between reinforcing fiber bundles. Is preferred. As the reinforcing fiber arranging mechanism, a known roller or comb-type arranging device can be used. It is also useful to stack a plurality of pre-arranged reinforcing fiber tapes from the viewpoint of reducing the gap between the reinforcing fibers. The creel is preferably provided with a tension control mechanism when drawing out the reinforcing fibers. As the tension control mechanism, a known mechanism can be used, and a brake mechanism or the like can be used. The tension can also be controlled by adjusting the thread guide. In the present invention, the reinforcing fiber bundles can be arranged to have a desired reinforcing fiber tape width.

On the other hand, specific examples of the reinforcing fiber fabric include, in addition to woven fabric and knitted fabric, those in which reinforcing fibers are two-dimensionally arranged in a multiaxial manner, and those in which reinforcing fibers such as nonwoven fabric, mat, and paper are randomly oriented. . In this case, the reinforcing fibers can be formed into a tape by using a method such as binder application, entanglement, welding, or fusion. As the woven fabric, a non-crimp woven fabric, a bias structure, an entangled woven fabric, a multiaxial woven fabric, a multiple woven fabric, or the like can be used in addition to the plain woven fabric, twill fabric, and satin woven fabric. The woven fabric combining the bias structure and the UD substrate not only suppresses the deformation of the woven fabric due to the tension in the coating / impregnation process due to the UD structure, but also has the pseudo-isotropy due to the bias structure, which is a preferable form. . In addition, the multi-layer fabric has an advantage that the structure / characteristics of the fabric upper / lower surface and the inside of the fabric can be individually designed. In the case of a knitted fabric, warp knitting is preferred in consideration of the shape stability in the coating / impregnation step, but a blade which is a tubular knitted fabric may 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 cut to have a desired width after forming the reinforcing fiber fabric. .

Among these, when giving priority to the mechanical properties of FRP, it is preferable to use a UD substrate, and the UD substrate can be produced by a known method in which reinforcing fibers are arranged in a tape shape in one direction. .

<How to use reinforced fiber tape containing coating liquid>
In recent years, in order to increase the efficiency of the prepreg laminating process, an apparatus called AFP (Automated Fiber Placement) for automatically laminating prepreg tapes has been widely used in aircraft applications and the like. It is important that the tape width be 3 to 30 mm (3 mm or more and 30 mm or less). Further, in a pressure vessel or the like, a manufacturing method called filament winding is conventionally used. At this time, a matrix resin is applied to one thread (tow) of a reinforcing fiber bundle in a resin tank, and the fiber is directly applied to a pressure vessel liner. This is wrapped around. When used for this purpose, the width of the reinforcing fiber tape is about the same as the tow of one yarn (usually about 6 to 12 mm). It can be as wide as 30 mm. A wide reinforcing fiber tape is preferable because, when the coating liquid-containing reinforcing fiber tapes are laminated, a gap between the tapes, that is, a portion where no reinforcing fibers are present, hardly occurs.

<Carbon fiber tape>
The carbon fiber tape in the present invention is a tape made of carbon fibers, which are reinforcing fibers, and may be formed from one bundle of carbon fibers or a plurality of carbon fiber threads.

As the carbon fibers, so-called carbonized yarns, graphite yarns obtained by known methods using various fibers such as acrylic, pitch-based, and cellulose-based fibers as precursors, surface-oxidized fibers thereof, and sizing treatments thereof 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 a precursor fiber of carbon fiber, a spinning method such as a wet type, a dry type, and a dry-wet type can be used.

In the wet spinning method, a solution in which a polyacrylonitrile homopolymer or copolymer is dissolved in a solvent can be used as the spinning solution. As the solvent, an organic solvent such as dimethylsulfoxide, dimethylformamide, and dimethylacetamide, and an aqueous solution of an inorganic compound such as nitric acid, sodium rhodanate, zinc chloride, and sodium thiocyanate are used.

The above spinning solution is spun through a spinneret, discharged into a spinning bath and solidified. As the spinning bath, an aqueous solution of the solvent used as a solvent for the spinning solution can be used. The fiber coagulated in the spin bath is washed with water and drawn to obtain a precursor fiber. The obtained precursor fiber is subjected to a flame-proofing treatment and a carbonization treatment as a firing step, and if necessary, further subjected to a graphitization treatment to obtain a carbon fiber. The heating temperature in the firing step is set at a maximum temperature of 1000 to 3000 ° C.

The carbon fiber tape can be obtained by forming the precursor fiber into a flat cross-sectional shape, for example, an oblong shape, and baking, or forming the obtained carbon fiber yarn bundle into a flat cross-sectional shape. Or a method of arranging a plurality of carbon fiber threads to obtain a tape-like shape.

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

(4) 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 electrolyte 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 and 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 bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, barium bicarbonate and ammonium bicarbonate; Ammonia, tetraalkylammonium hydroxide And an aqueous solution of hydrazine.

From the viewpoint that the covalent bond formation between the matrix resin and the oxygen-containing functional group on the carbon fiber surface is promoted and the adhesiveness is further improved, the carbon fiber tape is subjected to electrolytic oxidation treatment with an alkaline electrolyte, or the carbon fiber tape is acidified. After performing electrolytic oxidation treatment in an aqueous solution and subsequently washing with an alkaline aqueous solution, a matrix resin may be applied.

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, and carbonate. Aqueous solution of carbonate such as calcium, barium carbonate and ammonium carbonate; Aqueous solution of hydrogen carbonate such as sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, barium bicarbonate and ammonium bicarbonate; Aqueous solutions of alkyl ammonium and hydrazine are included. As a method of cleaning the carbon fiber tape with an alkaline aqueous solution, for example, a dipping method and a spraying method can be used.

After washing the carbon fiber tape with a liquid phase electrolytic oxidation treatment or an alkaline aqueous solution, it may be washed with water and dried.

<Sizing process>
A sizing treatment can also be performed on the carbon fiber tape in order to impart convergence to the obtained carbon fiber tape. The method of applying the sizing agent is not particularly limited, but using a coating device 100 described later is preferable because the sizing agent can be applied to the carbon fiber tape with high accuracy of the application amount and inside the tape. When the coating apparatus 100 is used, the carbon fiber tape may run in the vertical direction as shown in FIG. 1A, or may run in the horizontal direction as shown in FIG. 1B.

The sizing agent is used as an aqueous solution or aqueous dispersion, or an organic solvent solution. The sizing agent imparts convergence to the carbon fiber tape, improves bending resistance and abrasion resistance, and forms a composite of the carbon fiber tape. Any sizing agent can be used as long as it provides good composite material properties when used as a reinforcing fiber of the material.

The sizing agent used as an aqueous solution and / or aqueous dispersion may be added to a water-soluble resin such as polyalkylene oxide and its derivatives, polyvinylpyrrolidone and its derivatives, polyvinyl alcohol, and the like, or water-dispersible by adding various surfactants. And various known resins such as an epoxy resin and an unsaturated polyester resin.

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

Any organic solvent may be used as long as it can stably dissolve the resin.Examples include aromatic hydrocarbons such as benzene, toluene, and xylene, acetone, ketones such as methyl ethyl ketone, carbon tetrachloride, tricrene, and chloroform. Examples thereof include halogenated hydrocarbons and modified ethers such as cellosolve, but are not particularly limited to the above resins. What is necessary is just to select suitably according to a boiling point and industrial good handling. The organic solvent sizing agent may be used as a mixture of two or more kinds.

Specifically, the sizing comprises (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. More specifically, examples of the epoxy resin used in (A) include a glycidyl type epoxy resin and a non-glycidyl (peracetic acid) epoxy resin. The glycidyl type epoxy resin is a bisphenol type epoxy resin, for example, obtained by condensing epichlorohydrin with a bisphenol such as bisphenol A, bisphenol F, 2,2'-bis (4-hydroxyphenyl) butane. Phenol-based resins, for example, novolak-type phenolic resin treated with epichlorohydrin, and ester-based resins, such as glycidyl methacrylate and ethylenic double bond-containing monomer. Copolymer (eg, acrylonitrile, styrene, vinyl acetate, vinyl chloride). Examples of the non-glycidyl epoxy resin include a cyclic resin epoxy resin, 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. As the alkylene oxide adducts of bisphenols, the bisphenols described in (A) above can be used. -Alkylene oxide (ethylene oxide (EC), propylene oxide (PO), butylene oxide (BO), etc.) adducts (in the case of two or more alkylene oxide adducts, random or block adducts).

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

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

As described above, the production method of the present invention can be used as a method for applying a sizing agent to a carbon fiber tape. Further, it can be used as a method for applying a resin to a carbon fiber tape to which a sizing agent has been applied, as described later.

<Tension control of reinforcing fiber>
In the manufacturing method of the present invention, in order to uniformly pull out the reinforcing fibers stretched over the creel, and to improve the width accuracy of the reinforcing fiber tape, and eventually the coating solution-containing reinforcing fiber tape, the tension at the time of pulling out the reinforcing fibers from the creel is increased. It is preferable to control. For this purpose, the yarns are aligned and nipped, and a driving device is used to control the tension by providing a speed difference with the equipment in a later process. Alternatively, as described in JP-A-2005-248360, a direction changing guide roll is used. A driving method, a method using a roll connected with a powder brake as described in JP-A-2004-162055, and the like can be given. In addition, a creel having a brake mechanism in a spindle portion on which a reinforcing fiber bobbin is hung can be used. Examples of the brake mechanism include a band brake and an electromagnetic type. As the electromagnetic method, there is a method of providing magnetic torque control equipment using permanent magnets on a spindle shaft. Examples of the electromagnetic brake mechanism include those described in, for example, JP-A-2012-184076. Further, tension control can be performed via a dancer roll. Of these, it is preferable to use a creel provided with an electromagnetic brake mechanism from the viewpoint of precision of tension control and downsizing of the manufacturing apparatus.

<Smoothing of reinforcing fiber tape>
In the present invention, by increasing the smoothness of the surface of the reinforcing fiber tape, the uniformity of the application amount in the application section can be improved. For this reason, it is preferable to guide the reinforcing fiber tape to the liquid pool after smoothing the reinforcing fiber tape. The method of smoothing is not particularly limited, and examples thereof include a method of physically pressing with a facing roll or the like, and a method of moving a reinforcing fiber using an air flow. The physical pressing method is preferred because it is simple and does not easily disturb the arrangement of the reinforcing fibers. More specifically, calendering or the like can be used. The method using an air flow is preferable because it not only causes less abrasion but also has the effect of widening the reinforcing fiber tape.

<Widening of reinforcing fiber tape>
In the present invention, it is also preferable to guide the reinforcing fiber tape to the application section after the reinforcing fiber tape has been subjected to the widening process, from the viewpoint of efficiently producing a wide coating liquid-containing reinforcing fiber tape. If the tape width is large, it is considered that there is an advantage that the cover area at the time of laminating the prepreg tape is large and the gap at the time of lamination is suppressed. There is no particular limitation on the widening processing method, and 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, there is a method of bringing a reinforcing fiber sheet into contact with a vibrating roll as described in, for example, JP-A-2015-22799. As the vibration direction, when the traveling direction of the reinforcing fiber tape is the X axis, it is preferable to apply vibrations in the Y axis direction (horizontal direction) and the Z axis direction (vertical direction). It is also preferable to use them in combination. It is preferable that a plurality of projections are provided on the surface of the vibrating roll, because the abrasion of the reinforcing fibers by the roll can be suppressed. As a method using an air flow, see, 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, the reinforcing fiber tape is heated and then guided to the liquid pool, thereby suppressing the temperature drop of the tape and improving the viscosity uniformity of the coating liquid. This is preferred because The reinforcing fiber tape is preferably heated to a temperature close to the temperature of the coating liquid, and various heating means for this purpose include air heating, infrared heating, far-infrared heating, laser heating, contact heating, and heating medium heating (such as steam). Means can be used. Above all, infrared heating is preferable because the apparatus is simple and the reinforcing fiber tape can be directly heated, so that it can be efficiently heated to a desired temperature even at a high running speed.

<Coating liquid>
The coating liquid used in the present invention can be appropriately selected depending on the purpose to be applied. Examples of the coating liquid include a liquid containing a sizing agent and a surface modifying agent, such as a sizing agent and a surface imparting agent, which impart convergence and functionality, and a matrix resin for forming a prepreg tape.

マトリックス The matrix resin used in the present invention can be used as a resin composition containing various resins, particles, curing agents, and various additives described below. 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 directly laminated and molded to obtain a member made of FRP. The degree of impregnation can be controlled by the design of the application section and the additional impregnation after application. The matrix resin can be appropriately selected depending on the application, but it is common to use a thermoplastic resin or a thermosetting resin. The matrix resin may be a molten resin heated and melted or a matrix resin at room temperature. Further, a solution or a varnish formed using a solvent may be used. When the present invention is used for manufacturing a prepreg tape, the coating solution-containing reinforcing fiber tape may be referred to as a prepreg tape in some cases.

As the matrix resin, a resin generally used for FRP such as a thermoplastic resin, a thermosetting resin, and a photocurable resin can be used. Further, these may be used as they are if they are liquids at room temperature, or may be used as solids or viscous liquids at room temperature to reduce the viscosity by heating, or may be used as a melt by melting, or a solvent. May be used as a solution or varnish.

The thermoplastic resin is selected from a carbon-carbon bond, an amide bond, an imide bond, an ester bond, an ether bond, a carbonate bond, a urethane bond, a urea bond, a thioether bond, a sulfone bond, an imidazole bond, and a carbonyl bond in the main chain. 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), polyether sulfone (PES), polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyaryl ether ketone (PAEK), polyamide imide (PAI), etc. it can. In fields requiring heat resistance such as aircraft applications, PPS, PES, PI, PEI, PSU, PEEK, PEKK, PAEK, and the like are suitable. On the other hand, for industrial applications and automotive applications, polyolefins such as polypropylene (PP), PA, polyester, PPS, and the like are preferable in order to increase molding efficiency. These may be polymers or oligomers or monomers for low viscosity and low temperature coating. Of course, these may be copolymerized depending on the purpose, or they 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 terminal, a resin having a vinyl terminal, a resin having an allyl terminal, a resin having a nadic acid terminal, and a resin having a cyanate ester terminal. Can be These can be generally used in combination with a curing agent or a curing catalyst. In addition, these thermosetting resins can be appropriately used in combination.

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

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 a compound having an active group capable of reacting with an epoxy group. Preferably, a compound having an amino group, an acid anhydride group, or an azide group is suitable. Specifically, dicyandiamide, various isomers of diaminodiphenylsulfone, and aminobenzoic acid esters are suitable. More specifically, dicyandiamide is preferably used because of its excellent prepreg preservability. Further, various isomers of diaminodiphenyl sulfone are most suitable for the present invention because they give cured products having good heat resistance. As the aminobenzoic acid esters, trimethylene glycol di-p-aminobenzoate and neopentyl glycol di-p-aminobenzoate are preferably used. Although the heat resistance is lower than that of diaminodiphenyl sulfone, the tensile strength is lower. Because it is excellent, it is selected and used according to the application. It is also possible to use a curing catalyst if necessary. From the viewpoint of improving the pot life of the matrix resin, it is also possible to use a complexing agent capable of forming a complex with a curing agent or a curing catalyst.

In the present invention, it is also preferable to use a thermoplastic resin mixed with a thermosetting resin. A mixture of a thermosetting resin and a thermoplastic resin gives better results than using the thermosetting resin alone. This is because the thermosetting resin is generally capable of low pressure molding by an autoclave while having a brittle defect, whereas the thermoplastic resin is generally difficult to perform low pressure molding by an autoclave while having the advantage of being tough. This is because they exhibit a trade-off characteristic, that is, they can be used in combination to balance physical properties and moldability. When mixed and used, it is preferable to contain the thermosetting resin in an amount of more than 50% by mass from the viewpoint of the mechanical properties of the FRP obtained by curing the prepreg tape.

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

Ｔ Further, Tm is measured by a normal DSC at a heating rate of 10 ° C / min, and the peak top temperature of a peak-like signal corresponding to melting can be defined as Tm.

Further, it is preferable that the polymer particles do not dissolve in the matrix resin. As such polymer particles, for example, appropriate ones can be used with reference to the description in WO2009 / 142231 pamphlet and the like. More specifically, polyamide or polyimide can be preferably used, and polyamide, which can greatly improve impact resistance due to excellent toughness, is most preferable. Polyamides such as polyamide 12, polyamide 11, polyamide 6, polyamide 66, polyamide 6/12 copolymer, and the epoxy compound described in Example 1 of JP-A-01-104624 are semi-IPN (polymer interpenetrating network structure). Polyamide (semi-IPN polyamide) or the like can be suitably used. The shape of the thermoplastic resin particles may be a spherical particle, a non-spherical particle, or a porous particle, but a spherical shape is particularly preferable in the production method of the present invention since the flow characteristics of the resin are not deteriorated. Further, a spherical shape is a preferable embodiment 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.) and "Orgasol (registered trademark)" 1002D. , 2001UD, 2001EXD, 2002D, 3202D, 3501D, 3502D (all manufactured by Arkema Co., Ltd.), "Grillamide (registered trademark)" TR90 (manufactured by Mazaverke 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 of two or more.

In addition, when the demand for heat resistance of FRP is not severe, polyurethane-based, rubber-based, and core-shell rubber-based particles are used for the purpose of adjusting the rheological properties of the coating liquid or improving the toughness and vibration damping properties of FRP. It is also possible.

In order to increase the toughness of the FRP interlayer resin layer, it is preferable to keep the polymer particles in the reinforcing 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 still more preferably in the range of 10 to 30 μm. When the number average particle diameter is 5 μm or more, the particles do not enter the bundle of the reinforcing fibers, and can remain in the reinforcing 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 content in the obtained FRP can be optimized.

<Viscoelasticity of coating liquid>
It is preferable to select an optimum viscosity for the coating liquid used in the present invention from the viewpoint of processability and stability. Specifically, when the viscosity is in the range of 0.01 to 60 Pa · s, the dripping at the outlet of the constricted portion can be suppressed, and the high-speed running property and the stable running property of the reinforcing fiber sheet can be improved, which is preferable. When the coating liquid viscosity is 2 Pa · s or less, stable running is possible even when the running speed of the reinforcing fiber tape is 100 m / min or more, and the 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, more specifically, using a viscoelasticity measuring device such as a parallel disk type or cone type, distortion It is the viscosity at the coating liquid temperature measured at the liquid pool, measured at a speed of 3.14 s ^-1 . The loss elastic modulus can be measured in the same manner as the viscosity measurement described above, and is a loss temperature at a coating liquid temperature in the liquid reservoir and a strain rate of 3.14 s ^-1 .

Further, by controlling the viscoelasticity at 25 ° C., which is around room temperature, it is possible to reduce the adhesiveness of the coating liquid-containing reinforcing fiber tape. Accordingly, the coating liquid-containing reinforcing fiber tape is prevented from sticking to rolls and guides in the manufacturing process, and there is an advantage that the process can be stabilized. Furthermore, this makes it possible not only to release the coating liquid-containing reinforcing fiber tape directly without using a release tape or the like, but also to improve the unwinding property of the wound coating liquid-containing reinforcing fiber tape, High speed unwinding becomes possible. This is preferable when a prepreg tape is used as the coating liquid-containing reinforcing fiber tape, because high-speed lamination with an automatic laminating apparatus or the like becomes possible. Further, since the release tape is not used, the amount of the prepreg tape per winding package is increased, and the operation time of the automatic laminating apparatus can be extended, so that the laminating efficiency over 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 an aircraft, but also in a tow prepreg winding apparatus such as 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.

<Applying process by running the reinforcing fiber tape vertically downward>
The application process will be described with reference to FIG. 1A by taking a UD base material as an example. The method of applying the coating liquid 2 to the reinforcing fiber tape 1a in the coating apparatus 100 includes a method of applying a plurality of reinforcing fibers unwound from the creel 11. After the reinforcing fibers 1 are arranged in one direction (the depth direction of the 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 a detailed cross-sectional view of the application section 20 in FIG. 1 in an enlarged manner. The coating unit 20 includes

wall members

21a and 21b facing each other with a predetermined gap D therebetween, and a cross-sectional area between the

wall members

21a and 21b is continuous in a vertically downward Z (that is, a running direction of the reinforcing fiber tape). The liquid reservoir 22 which is gradually reduced, is located below the liquid reservoir 22 (on the side where the reinforcing fiber sheet 1a is carried out), and is smaller than the cross-sectional area of the upper surface of the liquid reservoir 22 (the side where the reinforcing fiber tape 1a is introduced). A slit-shaped constriction 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 coincides with the depth direction of the paper surface.

(4) In the application section 20, the reinforcing fiber tape 1a introduced into the liquid pool section 22 travels downward Z in the vertical direction while accompanying the surrounding coating liquid 2. At that time, since the cross-sectional area of the liquid reservoir 22 decreases in the vertical downward direction Z (the running direction of the reinforcing fiber sheet 1a), the accompanying coating liquid 2 is gradually compressed and moves toward the lower part of the liquid reservoir 22. As the pressure increases, the pressure of the coating liquid 2 increases. When the pressure in the lower part of the liquid reservoir 22 becomes higher, the accompanying liquid flow becomes more difficult to flow further downward, flows in the direction of the

wall members

21a and 21b, and is then blocked by the

wall members

21a and 21b and flows upward. Become like As a result, in the liquid reservoir 22, a circulating flow T is formed along the plane of the reinforcing fiber tape 1a and the wall surfaces of the

wall 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 circulating flow T and cannot approach the lower part of the liquid reservoir 22 or the narrowed portion 23 where the hydraulic pressure is large. As described further below, the air bubbles adhere to the fluff, and the fluff moves upward from the circulating flow T and passes near the upper liquid level 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 also it is possible to easily collect the retained fluff from the upper liquid surface of the liquid reservoir 22. Furthermore, when the reinforcing fiber tape 1a is run at a high speed, the fluid pressure further increases, so that the effect of eliminating fluff becomes higher. As a result, the coating liquid 2 can be applied at a high speed by the reinforcing fiber tape 1a, and productivity is greatly improved.

(4) The increased liquid pressure has an effect that the coating liquid 2 is easily impregnated into the inside of the reinforcing fiber tape 1a. This is based on the property (Darcy's law) that when a matrix material is impregnated into a porous body such as a reinforcing fiber bundle, the degree of impregnation increases with the pressure of the matrix resin. Also in this case, when the reinforcing fiber tape 1a is run at a higher speed, the hydraulic pressure is further increased, so that the impregnation effect can be further enhanced. The coating liquid 2 is impregnated with air bubbles / liquid replacement with the air bubbles remaining inside the reinforcing fiber tape 1a. The air bubbles pass through the gaps inside the reinforcing fiber tape 1a due to the above-mentioned liquid pressure and buoyancy, and the fibers are removed. It is discharged in the orientation direction (vertically upward). At this time, since the air bubbles are discharged without displacing the impregnated coating liquid 2, there is also an effect of not impairing the impregnation. Some of the air bubbles are discharged out of the surface (normal direction) from the surface of the reinforcing fiber tape 1a. However, the air bubbles are also quickly eliminated upward in the vertical direction by the above-mentioned liquid pressure and buoyancy. There is also an effect that the discharge of air bubbles proceeds efficiently without staying at the lower part of the liquid reservoir 22 having a high effect. Due to these effects, the reinforcing fiber tape 1a can be impregnated with the coating liquid 2 efficiently, and as a result, a high-quality coating liquid-containing reinforcing fiber tape 1b in which the coating liquid 2 is uniformly impregnated can be obtained. Becomes

Further, the reinforcing fiber tape 1a is automatically centered at the center of the gap D by the increased liquid pressure, and the reinforcing fiber tape 1a does not directly rub against the wall of the liquid reservoir 22 or 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 one of the gaps D due to a disturbance or the like, the coating liquid 2 is pushed into the narrower gap on the approaching side and compressed, so that the hydraulic pressure increases on the approaching side. Then, the reinforcing fiber tape 1a is pushed back to the center of the gap D.

The constriction 23 is designed to have a smaller cross-sectional area than the upper surface of the liquid reservoir 22. As can be understood from FIG. 2a, the cross-sectional area is reduced because the length of the pseudo plane made of the reinforcing fiber sheet in the perpendicular direction is small, that is, the interval between the members is small. This is because the impregnation and the self-centering effect can be obtained by increasing the fluid pressure at the constricted portion as described above. The cross-sectional shape of the uppermost surface of the constricted portion 23 should be made to match the cross-sectional shape of the lowermost surface of the liquid reservoir 22, from the viewpoint of the running property of the reinforcing fiber tape 1a and the flow control of the coating liquid 2. Although preferred, the constriction 23 may be slightly larger if necessary.

Here, in the application section 20 in 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. It is sufficient that the reinforcing fiber tape 1a is substantially vertically downward as long as the reinforcing fiber tape 1a can be stably and continuously driven.

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. For example, it is desired to increase the total amount of the coating liquid 2 applied to the reinforcing fiber tape 1a (to increase the basis weight). In this case, the

wall members

21a and 21b may be installed so that the gap D is widened.

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

As described later, in the application section 20, the reinforcing fiber tape 1a can be passed in a substantially horizontal or inclined direction. Whether the reinforcing fiber tape 1a is passed in the vertical downward direction, the horizontal direction, or the inclined direction can be determined depending on, for example, the space for installing the apparatus and the relationship with the preceding and following steps.

<Application process in which the reinforcing fiber tape runs in the horizontal or inclined direction>
With reference to FIG. 1b, a description will be given of a process of applying a matrix resin when the reinforcing fiber tape 1a travels in a horizontal direction or an inclined direction. The method of applying the matrix resin 2 to the reinforcing fiber sheet 1a in the coating apparatus 100 is as follows. After arranging the plurality of reinforcing fibers 1 unwound from 11 in one direction (in the depth direction of the paper) by the arrangement device 12 to obtain the reinforcing fiber tape 1a, the reinforcing fiber 1 is passed through the application unit 20 in the horizontal or inclined direction. Thus, 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 direction between the X direction and the Z direction in FIG. 1B. When the reinforcing fiber sheet 1a is introduced horizontally to the application section 20 as shown in FIG. 1B, the running 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. At this time, it is preferable to have a sealing mechanism for preventing the matrix resin 2 from leaking out at the introduction portion of the reinforcing fiber sheet 1a into the application portion 20.

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

Next, referring to FIGS. 2b to 2e, 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. FIG. 2b is a detailed cross-sectional view of the application section 20 in FIG. 1b in an enlarged manner. The application section 20 includes

wall members

21a and 21b facing each other with a predetermined gap D therebetween, and the wall members are integrated with the reinforcing fiber tape 1b introduction side and the exit side. Between the wall member 21a on the upper surface and the wall member 21b on the lower surface, a liquid reservoir 22 and a slit-shaped member which is located on the outlet side of the liquid reservoir 22 and has a smaller sectional area than the maximum portion of the liquid reservoir 22. A constriction 23 is formed.

(5) In the application section 20, the reinforcing fiber tape introduced into the liquid pool section 22 travels in the horizontal direction while accompanying the surrounding coating liquid 2. At this time, in the same manner as when the reinforcing fiber tape runs downward in the vertical direction, the coating applied in the area 22b of the liquid reservoir 22 where the cross-sectional area continuously decreases in the running direction of the reinforcing fiber tape. 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 reservoir 22 increases, the accompanying liquid flow becomes more difficult to flow in the outlet direction, flows in the direction perpendicular to the reinforcing fiber tape, and is then blocked by the

wall members

21a and 21b. Rarely, it flows in the direction opposite to the running direction of the reinforcing fiber tape. As a result, in the liquid reservoir 22, a circulating flow T is formed along the plane of the reinforcing fiber tape and the wall surfaces of the

wall members

21a and 21b. As a result, even if the reinforcing fiber tape brings the fluff into the liquid reservoir 22, the fluff moves along the circulating flow T and cannot approach the vicinity of the outlet of the liquid reservoir 22 having a high hydraulic pressure or the constriction 23. When the running speed of the reinforcing fiber tape is increased, the above-mentioned hydraulic pressure further increases, so that the effect of preventing the fluff from approaching the vicinity of the outlet or the constricted portion 23 is further increased, and the productivity is greatly improved.

Also, as in the case of running the reinforcing fiber tape vertically downward, the increased liquid pressure has an effect that the coating liquid 2 is easily impregnated into the inside of the reinforcing fiber tape. This is based on the property (Darcy's law) that when a matrix resin is impregnated into a porous body such as a carbon fiber bundle, 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 hydraulic pressure is further increased, so that the impregnation effect can be further enhanced. The coating liquid 2 is impregnated with bubbles remaining inside the reinforcing fiber tape by gas / liquid replacement, and the bubbles are continuously formed with the circulating flow T and the buoyancy so that the cross-sectional area is continuously reduced to the area 22a where the cross-sectional area is not reduced. A large amount comes near the boundary of the decreasing region 22b. For this reason, it is preferable to install a degassing mechanism 56 for degassing air bubbles from the coating liquid 2 near this.

Further, in the same manner as when the reinforcing fiber tape runs downward in the vertical direction, the reinforcing fiber tape is automatically centered in the center of the gap D by the increased hydraulic pressure, and the reinforcing fiber tape is moved to the liquid pool 22 or It does not directly rub against the wall surface of the stenosis portion 23, and has an effect of suppressing the generation of fluff here. This is because when the reinforcing fiber tape approaches one of the gaps D due to disturbance or the like, the matrix resin 2 is pushed into the narrower gap on the approaching side and compressed, so that the hydraulic pressure further increases on the approaching side. This is for pushing the reinforcing fiber tape back to the center of the gap D.

The constriction 23 is designed to have a smaller cross-sectional area than the largest part of the liquid reservoir 22. As can be understood from FIG. 2b, the cross-sectional area is reduced because the length in the perpendicular direction of the quasi-plane made of the reinforcing fiber tape is small, that is, the interval between the members is small. This is because the impregnation and the self-centering effect can be obtained by increasing the hydraulic pressure in the constricted portion 23 as described above. In addition, it is preferable that the cross-sectional shape of the inlet portion of the constricted portion 23 be made to match the cross-sectional shape of the surface of the liquid reservoir 22 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. Alternatively, the constriction 23 may be slightly larger if necessary.

Here, in the application section 20 of FIG. 2B, the reinforcing fiber tape runs completely in the horizontal direction, but is not limited to this, and the above-described effects of collecting fluff and discharging bubbles can be obtained, and the carbon fiber sheet 1a can be obtained. However, the vehicle may travel in the inclined direction in the application section 20 within a range in which the vehicle can travel stably continuously. Further, the application section 20 can be inclined.

Further, the total amount of the coating liquid 2 applied to the reinforcing fiber tape can be controlled by the gap D of the constricted portion 23 as in the case of running the reinforcing fiber tape vertically downward. 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.

FIG. 2B illustrates a case where one reinforcing fiber tape is introduced into the application section from the horizontal direction. However, introduction of the reinforcing fiber tape into the application section is not limited to this, and a plurality of reinforcing fiber tapes may be used as necessary. And the introduction direction may be the inclined direction. This will be described with reference to FIGS. 2c to 2e.

In FIG. 2C, one reinforcing fiber tape 1a runs obliquely downward from above, and is introduced into the coating unit 20 through the opening 60. Then, the running direction of the reinforcing fiber tape 1 a is changed in the horizontal direction by the direction changing member 61, and the reinforcing fiber tape 1 a is pulled out from the narrowed portion 23. Here, it is preferable that at least the surface of the direction changing member 61 that is in contact with the reinforcing fiber tape 1a is formed as a curved surface. Further, from the viewpoint of preventing winding of the reinforcing fiber tape 1a, the direction changing member 61 is preferably fixed. From these, it is preferable that the direction changing portion 61 is a fixed bar having a curved surface, and its cross-sectional shape can be exemplified by a circle, an ellipse, a saddle type, and the like. In addition, a curved surface and a flat surface may be mixed at a portion where the direction changing member 61 and the reinforcing fiber tape 1a are in contact with each other. However, if the ground start portion and the end portion of the reinforcing fiber tape 1a are curved surfaces, generation of fluff can be suppressed. ,preferable. Furthermore, when the traveling speed is particularly increased, a rotatable roller can be used from the viewpoint of suppressing abrasion between the reinforcing fiber tape 1a and the direction changing member 61.

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

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

In FIG. 2D, two reinforcing fiber tapes 1a run obliquely downward from above and are introduced into the coating unit 20 through the opening 60. The running direction of each of the two reinforcing fiber tapes 1a is changed by the direction changing member 61 to the horizontal direction, and after the two sheets are stacked, 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, the impregnation becomes easier in the region 22b and the constricted portion 23 where the cross-sectional area is continuously reduced, which is preferable.

Ｅ In FIG. 2e, two reinforcing fiber tapes 1a run obliquely downward from above and are introduced into the coating section 20 through the opening 60. Then, the impregnation of the two reinforcing fiber tapes 1a is advanced while passing through the plurality of direction changing members 61, and finally, the two sheets are pulled out from the constricted portion 23 after being laminated. At this time, the shape and number of the direction change members 61 for promoting the impregnation can be variously selected according to the purpose. In addition, the contact length between the direction changing member 61 and the reinforcing fiber tape 1a and the angle (wrap angle) formed between both ends of the contact portion 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 it is needless to say that any number of three or more reinforcing fiber tapes can be used.

FIG. 3 is a bottom view of the application unit 20 viewed from the direction of A in FIG. 2A. The coating section 20 is provided with

side wall members

24a, 24b for preventing the coating liquid 2 from leaking from both ends in the arrangement direction of the reinforcing fiber tape 1a, and is surrounded by the

wall members

21a, 21b and the

side wall members

24a, 24b. An outlet 25 of the constricted portion 23 is formed in the closed space. Here, the outlet 25 has a slit shape, and the 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 to be applied.

FIG. 4A is a cross-sectional view illustrating the structure inside the coating unit when the coating unit 20 is viewed from the direction B. In addition, the wall member 21b is omitted to make the drawing easy to see, and the reinforcing fiber tape 1a draws the reinforcing fibers 1 so as to be arranged with a gap therebetween. Arrangement without gaps is preferred from the viewpoint of the quality of the prepreg tape (one embodiment of the coating liquid-containing reinforcing fiber tape) and the mechanical properties of the FRP formed from the prepreg tape.

FIG. 4 b shows the flow of the coating liquid 2 in the gap 26. If the gap 26 is large, a vortex flows in the coating liquid 2 in the direction of R. Since the vortex flow R becomes a flow (Ra) directed outward at the lower portion of the liquid pool 22, the reinforcing fiber tape may be torn (breakage) or the interval between the reinforcing fibers may be increased. When a coating liquid-containing reinforcing fiber tape is used, there is a possibility that uneven arrangement of reinforcing fibers will occur. On the other hand, at the upper part of the liquid reservoir 22, the flow (Rb) flows inward, so that the reinforcing fiber tape 1a may be compressed in the width direction and the end thereof may be broken. In an apparatus represented by Patent Document 2 (Japanese Patent No. 3252278) for applying a coating liquid to both surfaces of an integral sheet-like base material (especially a film), a vortex flow in the gap 26 occurs. Also had little attention to quality.

Therefore, in the present invention, it is preferable to restrict the width of the gap 26 so as to suppress the generation of the vortex at the end. 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 constriction 23. It is preferable to configure so as to satisfy the following relationship.
L ≦ 1.1 × W.

As a result, generation of vortex flow at the ends is suppressed, cracks and breaks in 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, the coating liquid-containing reinforcing fiber tape 1b having high quality and high stability can be obtained. Furthermore, when this technique is applied to a prepreg tape, not only can the quality and quality of the prepreg tape be improved, but also the mechanical properties and quality of the FRP obtained using the prepreg tape can be improved.

Further, it is preferable to adjust the lower limit of L to be 0.9 × W or more. Controlling the distance L between the

side plate members

24a and 24b in this manner is also preferable from the viewpoint of improving the dimensional accuracy in the width direction of the coating liquid-containing reinforcing fiber tape 1b.

In addition, it is preferable that the width regulation is performed at least at the lower part of the liquid reservoir 22 (the position G in FIG. 4A) from the viewpoint of suppressing the generation of the vortex R due to the high liquid pressure below the liquid reservoir 22. Further, more preferably, when this width regulation is performed over the entire area of the liquid pool 22, the generation of the vortex flow R can be almost completely suppressed, and as a result, cracks and end breaks of the reinforcing fiber tape can be almost completely prevented. Can be suppressed.

In addition, from the viewpoint of suppressing the eddy flow in the gap 26, the width regulation may be performed only on the liquid pool portion 22, but when the constriction portion 23 is similarly performed, an excessive amount of the coating liquid is applied to the side surface of the coating liquid-containing reinforcing fiber tape 1b. It is preferable from the viewpoint of suppressing that 2 is given.

<Width regulation mechanism>
In the above description, the case where the

side wall members

24a and 24b play the width regulation is shown. However, as shown in FIG. 5A,

width regulation mechanisms

27a and 27b are provided between the

side wall members

24a and 24b, and the width regulation may be performed by such a mechanism. it can. This is preferable from the viewpoint that the width regulated by the width regulating mechanism can be freely changed so that a single application section can produce a coating liquid-containing reinforcing fiber tape having various widths. Here, the relationship between the width W (mm) of the reinforcing fiber tape immediately below the constriction 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. Controlling the width L2 regulated by the width regulating mechanism in this manner is also preferable from the viewpoint of improving the dimensional accuracy in the width direction of the coating liquid-containing reinforcing fiber tape 1b.

形状 The shape and material of the width regulating mechanism are not particularly limited, but a plate-shaped bush is simple and preferable. In the upper part, that is, in the place close to the liquid surface, the width smaller than the distance between the

wall members

21a and 21b (see FIG. 5a; the vertical direction of the width regulating mechanism in the "view from the Z direction"). By having this, the flow of the coating liquid in the horizontal direction can be prevented, which is preferable. On the other hand, from the middle part to the lower part of the width regulating mechanism, it is preferable that the shape conforms to the internal shape of the application part, because the retention of the coating liquid in the liquid pool part can be suppressed and the deterioration of the coating liquid can be suppressed. In this sense, it is preferable that the width regulating mechanism is inserted up to the constriction 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 follows the tapered shape of the liquid reservoir 22 and is inserted to the constriction 23. FIG. 5A shows an example in which L2 is constant from the liquid level to the outlet, but the width regulated by the portion may be changed within a range that achieves the purpose of the width regulating mechanism. The width regulating mechanism can be fixed to the application section 20 by an arbitrary method. In the case of a plate-shaped bush, by fixing the plate-shaped bush at a plurality of portions in the up-down direction, regulation 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 portion and to insert the lower portion into the application portion, since the width can be easily regulated by the width regulating mechanism.

<Width accuracy of coating fiber-containing reinforced fiber tape>
As described above, in the present invention, the running stability of the reinforcing fiber tape can be improved by various width restrictions in the application step, but similarly, the width accuracy of the coating liquid-containing reinforcing fiber tape can be improved thereby. . 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, a coating liquid containing reinforcing fibers tape width (W _n), measures the longitudinal direction of the tape 30 or more points. As a width measuring method, the obtained coating liquid-containing reinforcing fiber tape may be discretely measured using a caliper or the like off-line, or a moving image of the tape running below the coating section may be taken, and the tape width may be measured. Can be measured with a caliper or the like. Also at this time, measurement is performed discretely. In the case of discrete measurement, the distance between the measurement points is 30 cm or more in the longitudinal direction of the tape. Further, a width measuring device of an optical type or the like may be installed below the coating section to continuously measure the width. As the width measuring device, for example, LS-7030 manufactured by Keyence Corporation can be exemplified. In the case of continuous measurement, measurement is performed for 10 m or more in the longitudinal direction of the tape, and data (W _n ) of 30 points or more is obtained. Then, the average value (W _A ) and the standard deviation (σ _W ) of the tape width are obtained from these measured values (W _n ), and the width variation coefficient (CV) can be obtained from Expression (1).
CV (%) = (σ _W / W _A ) × 100 (%) (1).

In the method using a kiss roll as in Patent Literature 5, since the width of the reinforcing fiber tape is not regulated on the roll to which the coating liquid is applied, the reinforcing fibers easily move in the width direction due to the penetration of the coating liquid, and the width is essentially limited. Is likely to fluctuate. In fact, in Patent Document 5, the width regulating roll is operated after the application of the resin by the kiss roll, which is considered to indicate that the width accuracy on the kiss roll as the application portion is insufficient. On the other hand, in the present invention, as described above, the tape width can be controlled at the application portion by controlling the width L of the liquid pool portion or by adding a width regulating mechanism. It is done. If the width is regulated after the application of the matrix resin as in Patent Literature 5, it is predicted that there is a possibility that extra matrix resin will adhere to the width regulating portion, causing problems such as destabilizing the process and shortening the cleaning cycle. You. In contrast, when the width is regulated in the coating section as in the present invention, the coating liquid (such as a matrix resin) to be applied after the width restriction can be measured, so that there is a low possibility that the excess coating liquid will contaminate the downstream of the process. Is also an advantage.

<Cooling immediately after application>
As shown in FIG. 5b, it is also possible to cool the coating liquid-containing reinforcing fiber tape in a cooling step following the coating step. Here, that the coating step and the cooling step are continuous means that each step is performed without any 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 application increases the viscosity of the resin impregnated in the reinforcing fiber tape and suppresses the resin flow in the reinforcing fiber tape to maintain a good width accuracy. It is possible to The distance between the application section 20 and the cooling device 62 is not particularly limited, but the effect is higher as the distance is shorter, and preferably 500 mm or less. Although the form of the cooling device is not particularly limited, for example, a method in which air having a lower temperature than the coating liquid in the liquid pool portion is applied to the coating liquid-containing reinforcing fiber tape can be used.

<Shape of liquid pool>
As described in detail above, in the present invention, the liquid pressure can be increased in the running direction of the reinforcing fiber tape by continuously decreasing the cross-sectional area in the running direction of the reinforcing fiber tape in the liquid reservoir 22. It is important that the continuous reduction of the cross-sectional area in the running direction of the reinforcing fiber tape means that there is no particular limitation on the shape as long as the hydraulic pressure can be continuously increased in the running direction. In the cross-sectional view of the liquid reservoir, the liquid reservoir may have a curved shape such as a tapered shape (linear shape) or a trumpet shape. In addition, the cross-sectional area decreasing portion may be continuous over the entire length of the liquid pool portion, or may include a portion where the cross-sectional area does not decrease or a portion which expands conversely as long as the object and effects of the present invention can be obtained. You may go out. These will be described in detail below with reference to FIGS.

FIG. 6 is a detailed cross-sectional view of the application section 20b of another embodiment different from FIG. It is the same as the coating unit 20 of FIG. 2 except that the shapes of the

wall members

21c and 21d constituting the liquid pool 22 are different. As in the application part 20b of FIG. 6, the liquid reservoir 22 may be divided into a region 22a in which the cross-sectional area continuously decreases in the vertical direction Z downward, 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 is continuously reduced is preferably 10 mm or more. The vertical height H at which the more preferable cross-sectional area is continuously reduced is 50 mm or more. As a result, the distance in which the coating liquid 2 entrained by the reinforcing fiber tape 1a is compressed in the region 22a where the cross-sectional area of the liquid reservoir 22 is continuously reduced is secured, and the liquid generated at the lower part of the liquid reservoir 22 is secured. The pressure can be increased sufficiently. As a result, it is possible to prevent the fluff from clogging the narrowed portion 23 due to the hydraulic pressure, and to obtain the effect of impregnating the reinforcing fiber tape 1a with the coating liquid 2 by the hydraulic pressure.

Here, when the region 22a where the cross-sectional area of the liquid reservoir 22 is continuously reduced is tapered like the coating portion 20 in FIG. 2 or the coating portion 20b in FIG. 6, the opening angle θ of the taper is smaller. More specifically, it is preferable to form an acute angle (90 ° or less). Thereby, 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 a high liquid pressure can be easily obtained.

FIG. 7 is a detailed cross-sectional view of the application section 20c of another embodiment different from FIG. It is the same as the application section 20b of FIG. 6 except that the shape of the

wall members

21e and 21f constituting the liquid pool section 22 is a two-step tapered shape. As described above, the region 22a where the cross-sectional area of the liquid reservoir 22 is continuously reduced may be configured by a multi-stage taper portion of two or more stages. At this time, it is preferable to make the opening angle θ of the tapered portion closest to the constricted portion 23 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 is continuously reduced is 10 mm or more. The vertical height H at which the more preferable cross-sectional area is continuously reduced is 50 mm or more. As shown in FIG. 7, the area 22a where the cross-sectional area of the liquid reservoir 22 is continuously reduced is formed as a multi-stage tapered portion, so that the volume of the coating liquid 2 that can be stored in the liquid reservoir 22 is maintained while the constriction portion 23 is maintained. Can be further reduced. As a result, the liquid pressure generated in the lower part of the liquid reservoir 22 is further increased, and the effect of removing fluff and the effect of impregnating the coating liquid 2 can be further enhanced.

FIG. 8 is a detailed cross-sectional view of the application section 20d of another embodiment different from FIG. It is the same as the application section 20b in FIG. 6 except that the shape of the

wall members

21g and 21h constituting the liquid pool section 22 is stepped. As described above, if there is a region 22a in which the cross-sectional area is continuously reduced at the lowermost portion of the liquid reservoir 22, the effect of increasing the hydraulic pressure, which is the object of the present invention, can be obtained. May include a region 22c in which the cross-sectional area decreases intermittently. By forming the liquid reservoir 22 in a shape as shown in FIG. 8, the depth B of the liquid reservoir 22 can be increased and stored while maintaining the shape of the region 22 a where the cross-sectional area is continuously reduced. The volume can be increased. As a result, even when the coating liquid 2 cannot be continuously supplied to the coating section 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 can be reduced. Better.

FIG. 9 is a detailed cross-sectional view of the application unit 20e of another embodiment different from FIG. It is the same as the application section 20b in FIG. 6, except that the shape of the

wall members

21i and 21j forming the liquid pool section 22 is a trumpet shape (curved shape). In the application section 20b of FIG. 6, the area 22a where the cross-sectional area of the liquid pool section 22 is continuously reduced is tapered (straight), but is not limited to this. For example, as shown in FIG. May be. However, it is preferable that the lower part of the liquid pool part 22 and the upper part of the narrow part 23 are connected smoothly. This is because if there is a step at the boundary between the lower part of the liquid pool part 22 and the upper part of the narrow part 23, the reinforcing fiber sheet 1a is caught by the step, and there is a concern that fluff is generated at this part. When the region where the cross-sectional area of the liquid reservoir 22 is continuously reduced is a trumpet-like shape, the opening of the virtual tangent line at the lowermost part of the region 22a where the cross-sectional area of the liquid reservoir 22 is continuously reduced. It is preferable that the angle θ be an acute angle.

In the above description, an example in which the cross-sectional area is smoothly reduced has been described. However, in the present invention, the cross-sectional area of the liquid reservoir does not necessarily have to be smoothly reduced unless the object of the present invention is impaired.

FIG. 10 is a detailed cross-sectional view of the application unit 30 according to another embodiment different from the present invention. Unlike the embodiment of the present invention, the liquid reservoir 32 in 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 constriction 23 is discontinuous and sharp. It is a structure which reduces to. For this reason, the reinforcing fiber tape 1a is easily clogged.

It is also possible to improve the impregnation effect by contacting the reinforcing fiber tape with a plurality of bars in the application 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, and the higher the impregnation ratio. 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 step>
In the present invention, a resin film can be further provided to the coating liquid-containing reinforcing fiber tape 1b drawn from the coating step. Referring to FIG. 1, a resin film is supplied from the supply device 16 instead of the release tape 3, and the resin film can be laminated on the coating liquid-containing reinforcing fiber tape 1 b on the transport roll 14. In FIG. 1, the number of the resin film is one. However, it is of course possible to apply the resin film from both sides of the coating liquid-containing reinforcing fiber tape 1b, or one of them can be a release film. When two resin films are used, they may be the same resin film or different types of resin films. Further, the resin film may be a film coated on a support such as a release tape, or may be a film not containing the support.

において In the present invention, the resin used for the resin film is not particularly limited, and can be appropriately selected depending on 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 can 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 during high-speed running of the reinforcing fiber sheet. For this reason, when particles are applied in the resin film applying step, the high-speed running stability of the reinforcing fiber tape in the application step is improved, which is preferable. 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, so that it 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 to be formed into 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.

Alternatively, a certain resin component can be taken out of the matrix resin and formed 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, application stability can be improved by removing the thermoplastic resin from the matrix resin applied in the application step and applying the thermoplastic resin as a resin film to the coating liquid-containing reinforcing fiber tape. PES, PEI, PI, and the like are often used as such a thermoplastic resin. In addition, such a thermoplastic resin film may be a self-supporting film that does not require a support in some cases, and is useful from the viewpoint that the support can be omitted.

A resin film can be produced by a known method. For example, a film can be formed by using various known coaters such as a roll coater, a comma coater, a knife coater, a die coater, and a spray coater. Further, if necessary, a resin can be applied on a support such as a release sheet to form a film.

<Travel mechanism>
As a traveling mechanism for transporting the reinforcing fiber tape or the coating liquid-containing reinforcing fiber tape, a known roller or the like can be suitably used. In the present invention, since the reinforcing fiber tape is transported vertically downward, it is preferable to arrange rollers vertically above and below the application section.

In the present invention, the running path of the reinforcing fiber tape is preferably as straight as possible in order to suppress the arrangement disorder and fluffing of the reinforcing fibers. Further, the coating liquid-containing reinforcing fiber tape is often a sheet-like integral body which is a laminate with a release tape, but in the conveying step of this, if there is a bent portion, wrinkles due to a difference in the circumferential length between the inner layer and the outer layer. In some cases, the traveling path of the sheet-shaped integrated object is preferably as straight as possible. From this viewpoint, it is preferable to use a nip roll in the traveling path of the sheet-like integrated object.

Whether the S-shaped roll or the nip roll is used 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 that a high-tension take-off device for pulling out the coating liquid-containing reinforcing fiber tape from the application section is disposed downstream of the application section. This is because high frictional force and shear stress are generated between the reinforcing fiber tape and the coating liquid in the application section, and a high take-up tension is generated downstream in the process in order to overcome this and pull out the coating liquid-containing reinforcing fiber tape. This is because it is preferable to make them. A nip roll or S-shaped roll can be used as the high tension take-off device, but any of them can increase slipping force between the roll and the coating liquid-containing reinforcing fiber tape to prevent slip and enable stable running. It can be. For this purpose, it is preferable to arrange a material having a high friction coefficient on the roll surface, or to increase the nip pressure or the pressing pressure of the coating liquid-containing reinforcing fiber tape against the S-shaped roll. From the viewpoint of preventing the slip, the S-shaped roll is preferable because the frictional force can be easily controlled by the roll diameter and the contact length.

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

<Addition impregnation>
In order to adjust the degree of impregnation to a desired degree, it is also possible to combine a means for further increasing the degree of impregnation using an impregnating apparatus separately after coating with the present invention. Here, in order to distinguish it from the impregnation in the application section, additional impregnation after application is referred to as additional impregnation, and an apparatus therefor is referred to as an additional impregnation apparatus. 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 JP-A-2011-132389 and WO2015 / 060299, a laminate of a sheet-like carbon fiber bundle and a resin is preheated by a hot plate to sufficiently soften the resin on the sheet-like carbon fiber bundle. The impregnation can also be advanced by using a device that presses with a heated nip roll. The temperature of the hot plate for preheating, the surface temperature of the nip roll, the linear pressure of the nip roll, and the diameter and number of the nip rolls can be appropriately selected so as to obtain a desired impregnation degree. It is also possible to use an "S-wrap roll" in which a prepreg sheet runs in an S-shape as described in WO 2010/150022 pamphlet. In the present invention, “S-wrap roll” is simply referred to as “S-shaped roll”. WO 2010/150022 Pamphlet FIG. 1 shows an example in which the prepreg sheet runs in an S-shape, but if impregnation is possible, the contact length between the sheet and the roll, such as a U-shape, V-shape or Λ-shape, is described. May be adjusted. When the impregnation pressure is increased to increase the degree of impregnation, it is also possible to add an opposing contact roll. Further, as shown in FIG. 4 of the pamphlet of WO2015 / 076981, it is possible to improve the impregnation efficiency and increase the production speed of the prepreg by arranging the conveyor belt opposite to the “S-wrap roll”. Further, as described in WO 2017/068159 pamphlet or JP-A-2016-20397, it is also 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 impregnation device that vibrates a plurality of "ironing blades" with an ultrasonic generator. It is also possible to fold and impregnate the prepreg as described in JP-A-2013-22868.

<Simple additional impregnation>
In the above, the example of applying the conventional additional impregnation apparatus was shown, but the temperature of the coating liquid-containing reinforcing fiber tape may still be high immediately below the application section, and in such a case, after leaving the application section, it is not so much. If the additional impregnation operation is added before the time has passed, a heating device such as a hot plate for reheating the coating liquid-containing reinforcing fiber tape is omitted or simplified, and the impregnation device is greatly simplified and downsized. It is also possible. Such an impregnating device located immediately below the coating section is referred to as a simple additional impregnating device. As a simple additional impregnating device, a heated nip roll or a heated S-shaped roll can be used, but the roll diameter, the set pressure, and the contact length between the coating liquid-containing reinforcing fiber tape and the roll can be reduced as compared with a normal impregnating device. This is preferable because not only the size of the device can be reduced but also the power consumption and the like can be reduced.

離 Also, it is preferable that a release tape is applied to the coating liquid-containing reinforcing fiber tape before the coating liquid-containing reinforcing fiber tape enters the simple re-impregnation apparatus, because the running property of the coating liquid-containing reinforcing fiber tape is improved.

FIG. 13a shows an example of a process for producing a coating liquid-containing reinforcing fiber tape equipped with a supplemental impregnation device. A simple additional impregnating device 453 is provided immediately below the application section 430. Here, the simple additional impregnation device 453 shows an example of a nip roll, but the nip roller preferably has a heating mechanism. Further, the number of nip roll stages can be appropriately selected according to the purpose, but from the viewpoint of simplification of the process, three or less stages are preferable (FIG. 13a shows an example of two stages). In addition, it is preferable that the nip roller is provided with a driving device from the viewpoint of easily controlling the tension of the conveyance 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 nip roll surface is subjected to an appropriate release treatment so that the coating liquid-containing reinforcing fiber tape does not stick, or a release tape is inserted between the coating liquid-containing reinforcing fiber tape and the nip roll. (Not shown in FIG. 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 application 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. Is preferred. The separated release tape may be wound up as it is, or may be run again on the circuit so as to be inserted again from the application section 430 side.

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

FIG. 13A shows an example in which the simple additional impregnation and the application of the matrix resin film are directly led to the additional impregnation device 450.

<Winding>
In the present invention, the coating liquid-containing reinforcing fiber tape package can be formed by traversing and winding the coating liquid-containing reinforcing fiber tape, or by winding it into a disc shape. Known ones can be used according to the conditions.

Winders for traversing and winding are exemplified in, for example, JP-A-4-119123, JP-A-2008-37650, and JP-A-2012-12224.
In particular, when winding at a high speed of 100 m / min or more, using a bobbin traverse type winder makes it possible to straighten the yarn path of the coating liquid-containing reinforcing fiber tape. This is preferable because it can suppress bending, twisting, and turbulence at the package end face. A bobbin traverse type winder is exemplified in, for example, JP-A-2004-168466.

リール When winding in a disk shape, a reel-shaped winder using a roll with a collar or the like can be used.

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

The coating liquid-containing reinforcing fiber tape package wound with the coating liquid-containing reinforcing fiber tape has a bobbin shape such as a square end type, which is advantageous for large packaging, and improves the productivity of the manufacturing process of the coating liquid-containing reinforcing fiber tape. Not only that, the time required to replace the coating liquid-containing reinforcing fiber tape package in the post-process can be reduced, and the productivity in the post-process can be improved, which is preferable. Since the disk-shaped package has a straight yarn path, it is preferable because the coating liquid-impregnated reinforcing fiber tape hardly bends or twists, and the tape is hardly caught in both the 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 ratio of the matrix resin is desirably 10% or more. The state of impregnation of the matrix resin can be confirmed by tearing the collected prepreg tape and visually observing the inside, and more quantitatively, for example, 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 the adhesive tape is peeled off to separate the reinforcing fibers to which the matrix resin has adhered from the reinforcing fibers to which the matrix resin has not adhered. Then, the ratio of the mass of the reinforcing fibers to which the matrix resin has adhered to the mass of the entire reinforcing fiber tape charged 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 also be evaluated based on the water absorption due to capillary action. 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-T-2016-510077.

<Multiple lines>
FIG. 14 shows an example in which five application sections 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 application unit 430, respectively, to obtain five coating liquid-containing reinforcing fiber tapes 471, The reinforcing fiber preheating device 420 and the application unit 430 may be integrated in a parallel direction. In this case, the coating unit 430 may be provided with five independent width control mechanisms and five coating unit outlet widths.

Furthermore, as shown in FIG. 15, the entrance of the wide application section can be partitioned so as to obtain a desired tape width, and can be passed through the application section whose width has been adjusted. Further, as shown in FIGS. 16 and 17, it is also possible to displace the application sections in a horizontal direction or a vertical direction.

<Modifications and Variations of the Present Invention>
In the present invention, by using a plurality of coating sections, it is possible to further improve the efficiency of the manufacturing process and to enhance the functions.

For example, a plurality of application sections can be arranged so that a plurality of coating liquid-containing reinforcing fiber tapes are laminated. FIG. 18 shows, by way of example, an embodiment in which the coating liquid-containing reinforcing fiber tape is laminated using two application sections. The two coating liquid-containing reinforcing fiber tapes 471 pulled out from the first coating section 431 and the second coating section 432 pass through the direction change roll 445 and are stacked together with the release tape and the resin film 443 on the laminating roll 447 below. Stacking is also possible. When a release tape is positioned between the coating liquid-containing reinforcing fiber tape and the direction change roll, it is possible to suppress the prepreg from sticking to the nip roll and to stabilize the running, which is preferable. FIG. 18 exemplifies a device in which the release tape 446 is caused to travel on a circuit by two directional change rolls 445. Note that the direction changing roll can be replaced with a direction changing guide or the like that has been subjected to release processing. In FIG. 18, the high tension take-off device 444 is arranged after the lamination of the coating liquid-containing reinforcing fiber tape 471, 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 is produced. It is effective when you do. In addition, it is expected that the toughness and impact resistance of FRP will be improved by laminating thin prepreg tapes in multiple layers, and by applying this manufacturing method, thin multilayer prepreg tapes can be efficiently obtained. it can. Further, by easily laminating different types of prepreg tapes, a hetero-bonded prepreg tape having added functionality can be easily obtained. In this case, it is possible to change the type and fineness of the reinforcing fiber, the number of filaments, mechanical properties, fiber surface characteristics, and the like. Also, different matrix resins can be used. For example, a prepreg tape having a different thickness or a hetero-bonded prepreg tape obtained by laminating prepreg tapes having different mechanical properties can be used. In addition, a resin having excellent mechanical properties is provided in the first application section, and a resin having excellent tack properties is provided in the second application section. By laminating these, a prepreg tape capable of achieving both mechanical properties and tackiness can be easily obtained. Can be obtained. Conversely, it is also possible to arrange a resin having no tackiness on the surface. Alternatively, a resin without particles can be applied in the first application section, and a resin containing particles can be applied in the second application section.

As another mode, a plurality of application portions can be arranged in series in the running direction of the reinforcing fiber tape. FIG. 19 shows an example in which two application sections are arranged in series. It is preferable to dispose a high tension take-up device 448 between the first application unit 431 and the second application unit 432 from the viewpoint of stabilizing the running of the reinforcing fiber tape 416, but depending on the application conditions and the take-down conditions in the downstream of the process. Can be omitted. Further, when the release tape is positioned between the coating liquid-containing reinforcing fiber tape drawn out from the first application section and the high tension take-up device 448, the coating liquid-containing reinforcing fiber tape is prevented from sticking to the nip roll, and the running is suppressed. It can be stabilized and is preferable. 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.

こと By adopting such a series type 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, running stability, high-speed running performance, and the like can be improved by changing the application conditions depending on the application section. For example, a prepreg tape in which a matrix resin having excellent mechanical properties is provided in a first application section, and a matrix resin having excellent tack properties is provided in a second application section, and the mechanical properties and tack properties are compatible by laminating these. Can be easily obtained. Conversely, a matrix resin having no tackiness can be disposed on the surface. Alternatively, a resin without particles can be applied in the first application section, and a particle-containing matrix resin can be applied in the second application section.

いくつか As described above, several modes for disposing a plurality of application sections have been described. However, the number of application sections is not particularly limited, and various applications can be applied according to purposes. Of course, these arrangements can be combined. Furthermore, various sizes and shapes of the application section and application conditions (temperature, etc.) can be mixed and used.

As described above, the manufacturing method of the present invention is not only capable of improving the efficiency and stabilization of the manufacturing, but also is capable of improving the performance and functioning of the product, and is a manufacturing method excellent in scalability. The above shows an example in which the reinforcing fiber tape runs in the vertical direction.However, when the reinforcing fiber tape runs in the horizontal or inclined direction and the coating liquid is applied, the same simple additional impregnation and multiple lines are performed. And modifications.

As described above, the manufacturing method of the present invention is not only capable of improving the efficiency and stabilization of the manufacturing, but also is capable of improving the performance and functioning of the product, and is a manufacturing method excellent in scalability.

<Coating liquid supply mechanism>
In the present invention, the coating liquid is stored in the coating section, but it is preferable to appropriately supply the coating liquid because the coating proceeds. The mechanism for supplying the coating liquid to the coating unit is not particularly limited, and a known device can be used. It is preferable that the coating liquid is continuously supplied to the coating section because the running of the reinforcing fiber tape can be stabilized without disturbing the upper liquid level of the coating section. For example, self-weight can be supplied as a driving force from a tank storing the coating liquid, or can be supplied continuously using a pump or the like. As the pump, a gear pump, a tube pump, a pressure pump, or the like can be used as appropriate according to the properties of the coating liquid. When the coating liquid is solid at room temperature, it is preferable to provide a melter above the reservoir. Further, 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 amount of the coating liquid so that the liquid level above the coating portion of the coating liquid is as constant as possible. For this purpose, for example, a mechanism that monitors the liquid level, the weight of the application section, and the like and feeds it back to the supply device is conceivable.

<Online monitoring>
Further, it is preferable to provide a mechanism capable of online monitoring of the application amount for monitoring the application amount. The online monitoring method is not particularly limited, and a known method can be used. For example, as a device for measuring the thickness, for example, a beta-ray meter or the like can be used. In this case, the application amount can be estimated by measuring the thickness of the reinforcing fiber tape and the thickness of the coating solution-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 constricted portion 23. Application amount monitoring can of course be used as defect monitoring. As for 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 change roll 419, and the thickness of the prepreg is measured between the application section 430 and the direction change roll 441. Can be. 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, the width accuracy of the reinforcing fiber tape can be improved by drawing out the reinforcing fibers with a constant tension. It is preferable to use a creel provided with an electromagnetic brake mechanism at the spindle portion as a tension control device for pulling out the reinforcing fibers from the viewpoint of improving width accuracy and reducing the size of the entire device. The plurality of pulled out reinforcing fiber bundles 414 are orderly arranged by the reinforcing fiber arrangement device 415, and the reinforcing fiber tape 416 is formed. When one reinforcing fiber bundle is used as the reinforcing fiber tape, the reinforcing fiber arrangement device 414 may not be used. In FIG. 12a, only three yarns are drawn on the reinforcing fiber bundle, but in practice, one to several hundred yarns can be used. Thereafter, the sheet is conveyed vertically downward through a widening device 417, a smoothing device 418, and a direction change roll 419. In FIG. 12 a, the reinforcing fiber tape 416 is conveyed linearly between the reinforcing fiber arranging device 415 and the turning roller 419 between the devices. Note that the widening device 417 and the smoothing device 418 can be appropriately skipped or the devices can be omitted depending on the purpose. 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, and reaches the direction changing roll 441 via the reinforcing fiber preheating device 420 and the application unit 430. When a plurality of reinforcing fiber tapes are manufactured at the same time, the reinforcing fiber tape and the application section may be in one-to-one correspondence as shown in FIG. 14 or the inside of the wide application section is partitioned as shown in FIG. A reinforcing fiber tape may be passed therethrough. In addition, a plurality of application sections can be arranged in parallel as shown in FIG. 14, or can be arranged in a staggered manner as shown in FIG. Further, as shown in FIG. 17, it is also possible to arrange them in a staggered manner vertically. Further, the application section 430 can employ any shape of the application section as long as the object of the present invention is achieved. For example, the shapes as 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 can be provided in the application 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 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. Release paper, release film, or the like can be used for the release tape. The resin film and the release tape may be provided as needed, and in some cases, devices relating to these may be omitted. This can be taken off by the high tension take-up device 444. Immediately after the application, a cooling device may be provided as shown in FIG. 5B. In FIG. 12A, a nip roll is drawn as the high tension take-up device 444. When the coating liquid has a low viscosity or when the number of lines of the coating liquid-containing reinforcing fiber tape is small, the high tension take-off device can be omitted. Thereafter, the sheet-shaped integrated material passes through an additional impregnating device 450 provided with a hot plate 451 and a heating nip roll 452, is cooled by a cooling device 461, is taken off by a take-off device 462, and peels off the upper release tape 446. Then, a sheet-like integrated body 472 composed of a prepreg tape / a release tape can be obtained as a product. Additional impregnation may be performed as needed, and in some cases, an additional impregnating machine or a cooling device may be omitted. Since the sheet-like integrated object is conveyed in a basic straight line from the direction changing roll 441 to the winder 464, generation of wrinkles can be suppressed. As the winder, either traverse winding or disk winding can be used, but in the case of traverse winding, JP-A-4-119123, JP-A-2008-37650, and JP-A-2012-12224 can be used. For example, in order to suppress breakage or twisting of the coating liquid-containing reinforcing fiber tape, turbulence at the package end face, or the like, a guide or a traverse mechanism designed for the tape can be used. When the winding speed is set to 100 m / min or more, it is preferable to use a bobbin traverse type winder, but it may be selected in consideration of the layout, cost, and the like of the entire manufacturing apparatus. In FIG. 12A, illustrations of the matrix resin supply device and the online monitoring device are omitted.

FIG. 12A shows an example in which the reinforcing fiber tape runs in the vertical direction and is applied by the application unit 430. However, as shown in FIG. 12B, the application unit 430 has the form shown in FIGS. 1B and 2B to 2E. As in the case of 12a, the reinforcing fiber tape can be run in a horizontal direction or an inclined direction and applied. This is the same in the embodiment shown in FIG. 18 and FIGS. 13A and 19 to 22 described later.

FIG. 12c is a schematic view showing a sintering device 411b and subsequent steps in an example of a process and an apparatus for manufacturing a reinforcing fiber tape using the present invention. After passing through the surface treatment device 412b, the surface treatment agent drying device 413b, the sizing device 414b, and the sizing agent drying device 415b, it is conveyed vertically downward via the direction change roll 419. In the example shown in FIG. 12C, the reinforcing fiber tape 416 is linearly conveyed from the baking device 411b to the direction change roll 419 between the devices. Note that the widening device 417 and the smoothing device 418 can be appropriately skipped or the devices can be omitted depending on the purpose. Further, the arrangement order of the widening device 417 and the smoothing device 418 can be appropriately changed according to the purpose. Further, 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 depending on the required characteristics. The reinforcing fiber tape 416 travels vertically downward from the direction changing roll 419, and reaches the direction changing roll 441 via the reinforcing fiber preheating device 420 and the application unit 430. When a plurality of reinforcing fiber tapes are supplied at the same time, the reinforcing fiber tape and the application section may be in one-to-one correspondence as shown in FIG. 14, or the inside of the wide application section is partitioned as shown in FIG. A reinforcing fiber tape may be passed therethrough. In addition, a plurality of application sections can be arranged in parallel as shown in FIG. 14, or can be arranged in a staggered manner as shown in FIG. Further, as shown in FIG. 17, it is also possible to arrange them in a staggered manner vertically. Further, the application section 430 can employ any shape of the application section as long as the object of the present invention is achieved. For example, the shapes as 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 can be provided in the application 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 changing 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. Release paper, release film, or the like can be used for the release tape. The resin film and the release tape may be provided as needed, and in some cases, devices relating to these may be omitted. This can be taken off by the high tension take-up device 444. Immediately after the application, a cooling device may be provided as shown in FIG. 5B. In FIG. 12b, a nip roll is drawn as the high tension take-up device 444. When the coating liquid has a low viscosity or when the number of lines of the coating liquid-containing reinforcing fiber tape is small, the high tension take-off device can be omitted. Thereafter, the sheet-shaped integrated material passes through an additional impregnating device 450 provided with a hot plate 451 and a heating nip roll 452, is cooled by a cooling device 461, is taken off by a take-off device 462, and peels off the upper release tape 446. Then, a sheet-like integrated body 472 composed of a prepreg / release sheet as a product can be obtained by winding with a winder 464. Additional impregnation may be performed as needed, and in some cases, an additional impregnating machine or a cooling device may be omitted. Since the sheet-like integrated object is conveyed in a basic straight line from the direction changing roll 441 to the winder 464, generation of wrinkles can be suppressed. As the winder, either traverse winding or disk winding can be used, but in the case of traverse winding, JP-A-4-119123, JP-A-2008-37650, and JP-A-2012-12224 can be used. For example, in order to suppress breakage or twisting of the coating liquid-containing reinforcing fiber tape, turbulence at the package end face, or the like, a guide or a traverse mechanism designed for the tape can be used. In FIG. 12B, illustrations of the matrix resin supply device and the online monitoring device are omitted.

FIG. 12c shows an example in which the reinforcing fiber tape is run in the vertical direction following the baking process and is applied by the application unit 430. However, as shown in FIG. 12d, the application unit 430 is applied in the manner shown in FIGS. 1b and 2b to 2e. By doing so, it is possible to apply the reinforcing fiber tape by running it in the horizontal direction or the inclined direction. This is the same in the embodiment shown in FIG. 18 and FIG. 13b and FIGS.

FIGS. 13a and 13b are schematic views of another example of a prepreg tape manufacturing process / apparatus using the present invention. Here, an example using a simple additional impregnation device is shown. 13A and 13B, since the simple additional impregnating device 453 is installed immediately below the coating unit 430, the prepreg tape 471 is guided to the simple additional impregnating device 453 in a high temperature state. Can be 13A and 13B, the heating nip roll 454 is illustrated as an example, but a small heating S-shaped roll may be used depending on the purpose. The use of the simple additional impregnation apparatus is also advantageous in that the entire prepreg tape manufacturing apparatus can be made very compact. In particular, when the resin film 443 is a particle-containing resin film, it is preferable to increase the degree of impregnation of the prepreg tape because the particles in the resin film can be arranged on the prepreg tape surface layer in the next step.

FIG. 20 is a schematic view of another example of a prepreg tape manufacturing process / apparatus using the present invention. FIG. 19 shows an example in which a high tension take-off S-shaped roll 449 is used as a high tension take-off device, and two S-2 roll-type heated S-shaped rolls 455 are used as the additional impregnation device (two rolls-two sets in total). Although the drawing is performed, the number of rolls can of course be increased or decreased according to the purpose. Further, in FIG. 19, a 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 a prepreg manufacturing process / apparatus using the present invention. In this example, an example is shown in which a heated S-shaped roll of the "S-wrap roll" type 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 the following Examples 1 to 4, a reinforcing fiber tape using carbon fiber as a reinforcing fiber was used, a baking apparatus was attached, and a coating method was performed by a method of manufacturing a coating liquid-containing reinforcing fiber tape in which a baking step and a coating step were performed continuously. An example of obtaining a liquid-containing reinforcing fiber tape will be described.

<Example 1: Running vertically downward, with matrix resin A and sizing agent>
An apparatus having a configuration shown in FIG. 22B can be used as a resin-containing reinforcing fiber tape manufacturing apparatus. As the winder, a reel-type winder that winds up in a disk shape can be used. In FIG. 22B, illustrations of the coating liquid supply device and the online measurement device are omitted. In FIG. 22B, the direction change roll 441 is disposed between the winder 464 and the application section 430. However, the direction change roll 441 is removed, and the coating liquid-containing reinforcing fiber tape 471 coming out of the application section 430 is directly wound into the winder 464. You may wind it up.

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

炭素 As for the reinforcing fiber tape, a carbon fiber tape which has been subjected to the following steps (2) to (4) can be used. That is, (2) a step of spinning a copolymer of acrylonitrile and itaconic acid, and then performing calcination so that the maximum temperature reaches 1000 to 3000 ° C., and (3) a liquid phase using an aqueous solution of ammonium hydrogen carbonate as an electrolyte after calcination. After the electrolytic oxidation treatment, the carbon fiber subjected to the liquid phase electrolytic oxidation treatment is subsequently washed with water and dried in heated air, and (4) a sizing agent is applied to the carbon fiber tape after the surface oxidation treatment. And drying in heated air.

Then, using a mixture of an epoxy resin (a mixture of an aromatic amine-type epoxy resin and a bisphenol-type epoxy resin), a curing agent (dicyandiimide), and a curing aid (matrix resin A) as a matrix resin, a coating liquid-containing reinforcing fiber tape is used. Can be produced. The viscosity was measured using ARES-G2 manufactured by TA Instruments, at a measurement frequency of 0.5 Hz and a heating rate of 1.5 ° C./min, and was 0.6 Pa · s at 40 ° C. and 3 Pa at 25 ° C. -It is s. By using the matrix resin, 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 the coating liquid-containing reinforcing fiber tape.

連続 Evaluation of continuous running performance can be performed as follows. That is, the reinforcing fiber tape is allowed to run continuously for 30 minutes, and one having no fuzz clogging and thread breakage is referred to as “Good”, and one having fuzz clogged and thread breakage is referred to as “Bad”. In addition, in order to evaluate the signs of fuzz clogging, the coated portion is disassembled after continuous running for 60 minutes and 120 minutes and visually observed to check for fuzz. A fuzz attached to the vicinity of the constriction after continuous running is referred to as "poor", and a portion far from the constriction after continuous running (a boundary between a region where the cross-sectional area does not decrease and a region where the cross-sectional area decreases continuously). (Around) is referred to as a fuzz-preventing property “Fair”, and a case where no fuzz is adhered to the liquid contact surface of the wall member after continuous running is referred to as a fuzz-preventing property “Good”. Further, the vehicle was continuously run at a running speed of 10 m / min for 60 minutes, and the reinforcing fiber tape was cracked (a vertical streak-like sheet-like sheet) on the reinforcing fiber tape at the boundary between the area where the cross-sectional area did not decrease and the area where the cross-sectional area decreased continuously. The time during which the reinforcing fiber bundle travels uniformly without the tearing of the reinforcing fiber bundle) or the end portion of the reinforcing fiber tape (the portion where the reinforcing fiber bundle overlaps) is measured. "Excellent" means that the ratio of the time during which the fiber bundle is running uniformly without cracks and end breaks of the fiber bundle is 90% or more of the total running time, and "Good" means that the ratio is 50% or more and less than 90%. "10% or more and less than 50% is" Fair ", and less than 10% is" Poor ".

The first taper of the application section has an opening angle of 17 °, the second 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 obtained. When the running property at a running speed of 10 m / min is evaluated by changing H variously as 0 mm, when H ≧ 30 mm, there is no fluff and yarn clogging (Good), and the fuzz preventing property is Good. When 30 mm> H ≧ 10 mm, there is no fuzz or yarn clogging (Good), and the fuzz prevention property is Fair. When 10 mm> H ≧ 0 mm, the vehicle can run at 20 m / min, but the fuzz prevention property is poor. In addition, when the coating portion shown in FIG. 13 having no portion where the cross-sectional area continuously decreases (H = 0) is used, the reinforcing fiber sheet is clogged immediately after running at 10 m / min, and the continuous running property is improved. Becomes defective.

Next, assuming that H = 70 mm and variously changing the relationship L2 / W between the width L2 of the lower end portion of the width regulating mechanism and the width W of the coating liquid-containing reinforcing fiber tape, 1.1 × W <L2 (mm) is obtained. Cracking of reinforcing fiber tape is Bad, bending of end of reinforcing fiber tape Bad, 1.05 × W <L2 ≦ 1.1 × W (mm), cracking of reinforcing fiber tape is Good, end of reinforcing fiber tape In the case of bending Good, 0.8 × W ≦ L2 (mm), the crack of the reinforcing fiber tape is Excellent, and the end of the reinforcing fiber tape is Excellent.

より It can be seen that the smaller the L2 / W and the larger the H, the more stable the running of the coating liquid-containing reinforcing fiber tape. In addition, the impregnation rates by the peeling method are all 50 to 60%, which indicates that the impregnation is progressing in the application part. The impregnation rate by the peeling method is as follows: The collected coating liquid-containing reinforcing fiber tape is sandwiched between adhesive tapes, peeled off, and the carbon fibers to which the matrix resin is attached and the carbon fibers to which the matrix resin is not attached are separated. It is calculated from the ratio of the mass of the reinforcing fibers to which the matrix resin has adhered to the mass of the entire fiber tape.

Further, the uniformity of the coating 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 the longitudinal direction by 100 mm in a total length 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 fiber is measured as a residue obtained by eluting the resin from the coating solution-containing reinforcing fiber tape with a solvent. From this, when the average value of each value is calculated and the average value is compared with each value, it can be seen that both the carbon fiber and the resin fall within the range of ± 2% by mass, and that the uniformity in the longitudinal direction is excellent.

Further, when the width accuracy of the coating liquid-containing reinforcing fiber tape was evaluated, the number of data obtained at a measurement length of about 50 m was about 400, and the CV was about 4%, which was a good width accuracy.

In addition, no liquid is scattered in the coating process during coating, and no process contamination is observed.

<Example 2: Running in horizontal or inclined direction, matrix resin A, with sizing agent>
An apparatus having a configuration shown in FIG. 23 can be used as a resin-containing reinforcing fiber tape manufacturing apparatus. That is, the application section runs the reinforcing fiber tape in an oblique direction (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 other parts are the same as Example 1 except for the application section. 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 unit and the winder can be removed as in Example 1. Further, the same matrix resin as in Example 1 can be used.

The first-stage taper of the application section has an opening angle of 17 °, the second-stage taper has an opening angle of 7 °, H = 70 mm, L2 = W × 1 (mm), running of a reinforcing fiber tape and a coating liquid-containing reinforcing fiber tape. When the coating liquid-containing reinforcing fiber tape was prepared at a speed of 10 m / min and the running property was evaluated, there was no fuzz or yarn clogging (Good), and the fuzz preventing property was Good. Further, the impregnation degree by the peeling method is about 55%, and the uniformity of the basis weight in the longitudinal direction is within the range of ± 2%, which is good.

<Example 3: Running vertically downward, matrix resin A, no sizing agent>
An apparatus having a configuration shown in FIG. 24 can be used as a resin-containing reinforcing fiber tape manufacturing apparatus. As the winder, a reel-type winder that winds up in a disk shape can be used. In FIG. 24, the illustration of the coating liquid supply device and the online measurement device is omitted. The direction changing roll between the application section and the winder can be removed in the same manner as in Example 1, the application section is the same as in Example 1, and the coating liquid can use the matrix resin A as in Example 1. .

Reinforced fiber tape that 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 performing calcination so that the maximum temperature of the heating temperature is 1000 to 3000 ° C., and (3) using an aqueous solution of ammonium hydrogen carbonate as an electrolyte after calcination. After the liquid phase electrolytic oxidation treatment, the reinforcing fiber tape subjected to the liquid phase electrolytic oxidation treatment is successively washed with water and dried in heated air.

The first-stage taper of the application section has an opening angle of 17 °, the second-stage taper has an opening angle of 7 °, H = 70 mm, L2 = W × 1 (mm), running of a reinforcing fiber tape and a coating liquid-containing reinforcing fiber tape. When the coating liquid-containing reinforcing fiber tape was prepared at a speed of 10 m / min and the running property was evaluated, there was no fuzz or yarn clogging (Good), and the fuzz preventing property was Good. The cracking of the reinforcing fiber tape was Excellent and the end of the reinforcing fiber tape was broken, but compared with the same conditions in Example 1 (H = 70 mm, L2 = W × 1 (mm)), Example 3 There were many cracks and end breaks in the tape. Further, 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%.

<Example 4: Running vertically downward, with matrix resin B and sizing agent>
An apparatus having a configuration shown in FIG. 25 can be used as a resin-containing reinforcing fiber tape manufacturing apparatus. That is, in addition to the apparatus of Example 1, an apparatus configuration mainly including a release tape supply apparatus, a high tension take-up apparatus, an additional impregnation apparatus, a cooling apparatus, a take-up apparatus, and a winder can be used. In FIG. 25, the illustration of the coating liquid supply device and the online measurement device is omitted. In addition, the application 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 application part so that the temperature and viscosity of the matrix resin can be adjusted while measuring the temperature with a thermocouple. Can be.

炭素 With respect to the reinforcing fiber tape, a carbon fiber tape that has undergone the following steps (2) and (3) can be used. That is, (2) a step of spinning a copolymer of acrylonitrile and itaconic acid, and then performing calcination so that the maximum temperature reaches 1000 to 3000 ° C., and (3) a liquid phase using an aqueous solution of ammonium hydrogen carbonate as an electrolyte after calcination. After the electrolytic oxidation treatment, a step of successively washing the carbon fiber tape subjected to the liquid phase electrolytic oxidation treatment with water and drying in a heated air.

Using a mixture of an epoxy resin (a mixture of an aromatic amine-type epoxy resin and a bisphenol-type epoxy resin), a curing agent (diaminodiphenylsulfone), and a polyethersulfone (matrix resin B) as a matrix resin, the coating liquid content is strengthened. A fiber tape can be made. The viscosity was measured using ARES-G2 manufactured by TA Instruments at a measurement frequency of 0.5 Hz and a heating rate of 1.5 ° C./min. As a result, 50 Pa · s at 5 ° C. and 15 Pa · s at 90 ° C. 4 Pa · s at 105 ° C. By using the matrix resin, the temperature of the matrix resin in the application section 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 first-stage taper of the application section has an opening angle of 17 °, the second-stage taper has an opening angle of 7 °, H = 70 mm, L2 = W × 1 (mm), and the matrix resin temperature of the application section is 90 ° C. When the running speed of the fiber sheet and the reinforcing fiber tape is set at 10 m / min to prepare a coating liquid-containing reinforcing fiber tape, and the running property is evaluated, there is no fuzz or yarn clogging (Good), and the fuzz prevention property is Good. Further, the impregnation degree by the peeling method is about 55%, and the uniformity of the basis weight in the longitudinal direction is within the range of ± 2%, which is good.

<Prepreg tape manufacturing equipment>
The apparatus having the configuration shown in FIG. 22A was used as a prepreg manufacturing apparatus. A creel provided with an electromagnetic brake mechanism was used. As a winder, a reel-type winder wound up in a disk shape was used. Here, additional impregnation was not performed. In FIG. 22A, illustrations of the coating liquid supply device and the online measurement device are omitted.

<Coating part>
An application unit of the application unit 20b type shown in FIG. 6 was used. In the application part, a stainless steel block was used for the wall member forming the liquid pool part and the constricted part, and a stainless steel plate was used for the side plate member. To further 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 reservoir was 30 °. Further, as the width regulating mechanism, a plate-shaped bush adapted to the inner shape of the application section as shown in FIG. 5A is provided, and the installation position of the plate-shaped bush is changed freely so that L2 can be adjusted appropriately. L2 was set to 10 mm. The gap D at the stenosis was 0.2 mm. In addition, in order to prevent the coating liquid from leaking from the stenotic portion outlet, the lower surface of the stenotic portion outlet was closed with the outside of the bush being used.

<Reinforcing fiber tape>
The following were used as the reinforcing fibers.
Reinforcing fiber 1: carbon fiber (Toray's “Treca (registered trademark)” T800S (24K))
Reinforcing fiber 2: carbon fiber (Toray's “Treca (registered trademark)” T720S (36K))
Then, one yarn of the 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 polyether sulfone was used.

The viscosity was measured using ARES-G2 manufactured by TA Instruments at a measurement frequency of 0.5 Hz and a heating rate of 1.5 ° C./min, and was 15 Pa · s at 90 ° C. and 200 Pa · s at 60 ° C. 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 assistant. The viscosity was measured using ARES-G2 manufactured by TA Instruments at a measurement frequency of 0.5 Hz and a heating rate of 1.5 ° C./min, 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 in the application section of the reinforcing fiber sheet, the running was continuously performed for 30 minutes, and those having no fuzz clogging and thread break were designated as "Good", and those having fuzz clogged and thread broken were designated as "Bad".

Also, in order to evaluate the signs of fuzz clogging, the coating portion was disassembled after continuous running for 60 minutes and 120 minutes, and the liquid contact surface of the wall member was visually observed to check for the presence of fuzz. The fuzz-preventing property “Poor” is used for the case where fuzz is attached near the constriction after continuous running, and the case where fuzz is attached to the portion far from the constriction 23 (near the upper part of the liquid reservoir 22) after continuous running. The fuzz-preventing property was evaluated as “Fair”, and the fuzz-preventing property “Good” was evaluated when no fuzz was attached to the liquid contact surface of the wall member 21 after continuous running.

Further, the fiber was continuously run at a running speed of 20 m / min for 60 minutes, and the fiber bundle was broken (a portion where the sheet-like carbon fiber bundle was torn in a vertical streak) or the end of the fiber bundle was broken in the reinforcing fiber sheet immediately above the liquid pool. The time during which there was no (the portion where the carbon fiber bundles overlapped) running uniformly was measured. "Excellent" means that the ratio of the time during which the fiber bundle is running uniformly without cracks and end breaks of the fiber bundle is 90% or more of the total running time, and "Good" means that the ratio is 50% or more and less than 90%. "10% or more and less than 50% were designated as" Fair ", and those less than 10% were designated as" Poor ".

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

<Evaluation of prepreg tape width accuracy>
An optical width measuring device (LS-7030) manufactured by KEYENCE CORPORATION was installed immediately below the coating section, and the width of the prepreg tape was continuously measured in the process, and was taken into a data logger. From the obtained data, the CV value of the prepreg tape width was calculated.

[Examples 1 to 4]
A prepreg tape was produced by using CF1 as the reinforcing fiber and matrix resin A as the coating liquid, setting the matrix resin temperature in the application section to 90 ° C. and the running speed of the reinforcing fiber tape to 20 m / min. Relationship between the width L2 of the lower end of the width regulating mechanism and the width W of the prepreg tape L2-W and the running stability of the prepreg tape in the coating section when the height H at which the cross-sectional area of the coating section continuously decreases is variously changed. Table 1 shows the evaluation results.

From this, it can be seen that the larger the H and the smaller the L2-W, the better the running stability and the fuzz prevention properties.

Further, when the width accuracy of the prepreg tape was evaluated, as shown in Table 1, in Examples 1 to 4, CV = 5% or less, which was a good width accuracy. The number of measured tape widths for obtaining the CV value will be described. The number of acquired data was 427 / 57.2 m.

Further, in all the examples, the impregnation rate was 50% or more, and it was confirmed that the impregnation was advanced. The resin content in the entire prepreg tape was about 25% by mass.

[Comparative Example 1]
A prepreg was prepared in the same manner as in Example 1 under the conditions shown in Table 1 by using a coating portion having no portion where the cross-sectional area shown in FIG. 10 continuously decreases (H = 0). Minutes after the start of running, the reinforcing fiber sheet was immediately clogged, and the continuous running performance was poor.

[Comparative Example 2]
A prepreg tape was produced 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 regulating mechanism and the width W of the prepreg tape was set to 2 mm. When the width accuracy of the prepreg tape was evaluated, CV was 6%, and the width accuracy was not as high as in Examples 1 to 4, and the tape width fluctuation was large. When the prepreg tapes were laminated, the tapes were overlapped, and there was a possibility that local thickness defects occurred. The number of acquired data was 427 / 57.2 m.

[Example 5]
As the prepreg manufacturing apparatus, an apparatus having the configuration shown in FIG. 22C and further including a cooling device 433 in the apparatus having the configuration shown in FIG. 22A was used. A prepreg tape was produced by using CF1 as the reinforcing fiber and matrix resin A as the coating liquid, setting the matrix resin temperature in the application section to 90 ° C. and the running speed of the reinforcing fiber tape to 20 m / min. The temperature of the coating liquid-containing reinforcing fiber tape after the cooling device 433 was 60 ° C. The relationship L2-W between the width L2 of 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 Example 4. Table 2 shows the results. When the width accuracy of the prepreg tape was evaluated, CV was 4%, and the width accuracy was improved as compared with Example 4 by using the cooling device.

[Example 6]
A prepreg tape was prepared by using CF2 as the reinforcing fiber and matrix resin B as the coating liquid, setting the matrix resin temperature in the application section to 40 ° C and the running speed of the reinforcing fiber tape to 125 m / min. The relationship L2-W between the width L2 at 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 was continuously reduced was 50 mm.

At this time, stable running was possible at 125 m / min for 30 minutes or more without fuzz clogging or thread breakage. Also, no cracks or breaks were found at the end of the tape.

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

In addition, when the prepreg tape was unwound from the obtained prepreg tape winding package, the prepreg tape surface showed almost no tackiness, and despite the absence of a support such as a release tape, the prepreg tape was unwound. The washability 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, such as structural materials and interior materials for aerospace applications, automobiles, trains and ships, pressure vessels, industrial materials applications, and sports. It can be widely used for materials, medical equipment, housing, civil engineering and construction.

REFERENCE SIGNS LIST 1 Reinforcing fiber 1a Reinforcing fiber tape 1b Reinforcing fiber tape containing coating liquid 2 Coating liquid 3 Release tape or resin film 11 Creel 11a Firing device 12 Arranging

device

13, 14 Transport roll 15 Winding device 16, 16a, 16b Supply device 20 Coating Unit 20b Coating unit 20c of another embodiment Coating unit 20d of another embodiment Coating unit 20e of another

embodiment Coating units

21a, 21b of another

embodiment Wall members

21c,

21d Wall members

21e, 21f of different

shapes Wall members

21g, 21h having different

shapes Wall members

21i, 21j having different shapes 22 Wall members 22 having different shapes Liquid reservoir 22a A region 22b of the liquid reservoir where the cross-sectional area is continuously reduced. Area 22c where the area does not decrease Area 23c where the cross-sectional area is reduced intermittently in the liquid reservoir

part Narrowing parts

24a and 24b Side plate member 5 Outlet 26

Gap

27, 27a, 27b Width regulating mechanism 30

Coating portions

31a, 31b of Comparative example 1 Wall member 32 of Comparative example 1 Liquid reservoir 33 of Comparative example 1 Cross section of liquid reservoir of Comparative example 1 is

intermittent Bars

35a, 35b, 35c Bar 56 Deaeration mechanism 60 Opening 61 Direction changing member 62 Cooling device 100 Coating device B Depth of liquid reservoir 22 Height D to upper liquid surface of liquid reservoir 22 Gap G of the constricted portion G Position for controlling the width H Vertical height L where the cross-sectional area of the liquid reservoir 22 continuously decreases Width R, Ra, Rb of the liquid reservoir 22 Vortex flow T Circulation flow U of the constricted portion 23 Width W The width X of the coating liquid-containing reinforcing fiber tape measured just below the constricted portion 23. The horizontal direction Y X, the direction perpendicular to Z. The running direction of the reinforcing fiber tape 1a (vertically downward).
θ Taper opening angle 411 Creel 411b Firing device 412 Reinforcing fiber bobbin 412b Surface treatment device 413 Direction changing guide 413b Drying device for surface treatment agent 414 Reinforcing fiber bundle 414b Sizing device 415 Reinforcing fiber arrangement device 415b Drying device for sizing agent 416 Reinforcement Fiber tape 417 Widening device 418 Smoothing device 419 Direction change roll 420 Reinforcement fiber preheating device 430 Application section 431 First application section 432 Second application section 433 Cooling device 441 Direction change roll 442 Release tape or resin film supply device 443 Release tape or resin film 444 High tension take-up device 445 Direction change roll 446 Release tape 447 Laminate roll 448 High tension take-up device 449 High tension take-off S-shaped roll 450 Additional impregnating device 451 Hot plate 452 Heating nip Roll 453 Simple add impregnator 454 heated nip roll 455 heated S-roll 456 contact roller 461 cooling system 462 taking over device 463 release the tape (upper) winding device 464 winder 471 prepreg (coating liquid containing reinforcing fibers tape)
472 Pre-preg / release tape (sheet-like integrated material)

Claims

A method for producing a coating liquid-containing reinforced fiber tape obtained by applying a coating liquid to the reinforced fiber tape by passing a reinforced fiber tape having a tape width of 3 to 30 mm through the inside of the application section in which the coating liquid is stored. hand,
The coating unit includes a liquid reservoir and a constricted portion communicated with each other,
The liquid reservoir has a portion whose cross-sectional area is continuously reduced along the running direction of the reinforcing fiber tape,
The constricted 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 reinforcing fiber tape drawn out from the constricted portion is 5% or less. is there,
A method for producing a coating liquid-containing reinforcing fiber tape.
2. The coating according to claim 1, further comprising a firing step in which the maximum temperature reaches 1000 to 3000 ° C., and wherein at least the step from the firing step to the step of applying the coating liquid to the reinforcing fiber tape is performed continuously. A method for producing a liquid-containing reinforcing fiber tape.
The length of the portion where the cross-sectional area in the liquid reservoir is continuously reduced is 10 mm or more,
A method for producing the coating liquid-containing reinforcing fiber tape according to claim 1.
The method for producing a coating liquid-containing reinforcing fiber tape according to any one of claims 1 to 3, wherein the coating liquid is applied to the reinforcing fiber tape by passing the reinforcing fiber tape substantially downward in the application section. .
The coating liquid-containing reinforcing fiber tape according to any one of claims 1 to 3, wherein the coating liquid is applied to the reinforcing fiber tape by passing the reinforcing fiber tape substantially horizontally or in an inclined direction in the application section. Production method.
The width L (mm) of the lower part of the liquid pool part in the tape width direction of the reinforcing fiber tape and the width W (mm) of the tape-like reinforcing fiber immediately below the constriction part satisfy L ≦ 1.1 × W. 6. The method for producing a coating liquid-containing reinforcing fiber tape according to any one of 1 to 5.
A width regulating mechanism for regulating the width of the reinforcing fiber tape is provided in the liquid reservoir, and the width W (mm) of the reinforcing fiber tape immediately below the constriction and the width L2 regulated by the width regulating mechanism at the lower end of the width regulating mechanism. 7. The method for producing a coating liquid-containing reinforcing fiber tape according to claim 1, wherein a relationship with (mm) satisfies L2 ≦ 1.1 × W (mm).
(8) The method for producing a coating liquid-containing reinforcing fiber tape according to any one of (1) to (7), wherein the viscosity of the coating liquid is 2 Pa · s or less.
The method for producing a coating liquid-containing reinforcing fiber tape according to any one of claims 1 to 8, wherein the additional impregnation is performed on the coating liquid-containing reinforcing fiber tape pulled out from the constriction.
The coating liquid-containing reinforcing fiber tape according to any one of claims 1 and 3, wherein the reinforcing fiber tape is introduced into the application section after being pulled out using a creel provided with an electromagnetic brake mechanism. Production method.
A method for producing a coating liquid-containing reinforcing fiber tape package, wherein the coating liquid-containing reinforcing fiber tape according to any one of claims 1 to 10 is traversed and wound.
12. A method for producing a coating liquid-containing reinforcing fiber tape package, comprising winding the coating liquid-containing reinforcing fiber tape according to any one of claims 1 to 11 into a disc shape.
The method for producing a coating liquid-containing reinforcing fiber tape package according to claim 11 or 12, wherein only the coating liquid-containing reinforcing fiber tape is wound.