CN1078633C - Resin coating reinforced fiber filament, formation material and mfg. method thereof - Google Patents

Abstract

The present invention relates to a method for producing resin-coated reinforcing fiber filaments, characterized in that a reinforcing fiber bundle formed of a plurality of reinforcing continuous fibers is in a moving state, and is arranged from a place surrounding the reinforcing fiber bundle but not in contact with the reinforcing fiber bundle The ring-shaped nozzle at the position extrudes the molten thermoplastic resin into a hollow cylinder. in a stress-free state. A thermoplastic resin is applied by contacting the outer periphery of the above-mentioned reinforcing fiber bundle; a resin-coated reinforcing fiber filament is obtained.

Description

Method for producing resin-coated reinforcing fiber filaments

The present invention relates to a resin-coated reinforcing fiber yarn for forming a reinforced thermoplastic resin molded body on continuous fibers and a method for producing the resin-coated reinforcing fiber yarn.

In the past, thermoplastic resin moldings reinforced with continuous fibers have been widely used due to the advantage of a large reinforcing effect. In order to make such a continuous fiber reinforced thermoplastic resin molded body, the thermoplastic resin is usually impregnated on the reinforcing fiber to form a laminate, and the method of heating and pressing is formed. The fabric formed on the reinforcing fiber filament and thermoplasticity A method in which resin films are laminated by intersecting each other and formed by heat and pressure, or a method in which a braided fabric of reinforcing fiber filaments and thermoplastic resin fibers is laminated and formed by heat and pressure, etc. However, when a film or a thin plate is used as a laminate material, the moldability in three-dimensional shape molding is not good. Furthermore, when fabrics are used, the resin impregnation properties of the reinforcing fibers are not good, especially at the intersecting points of the reinforcing fibers in the fabrics, the resin impregnation properties are even worse. In addition, when weaving reinforced fiber filaments, the fibers are easily damaged, and the number of single fibers constituting one reinforced fiber filament should not be too many (for example, with glass fibers with a single filament diameter of 7 μm, the limit is about 6000), and it cannot be achieved. Increase the number of single fibers to increase productivity.

Therefore, in order to improve the resin impregnation, it is proposed to make filaments (bundles, yarns, etc.) containing continuous fibers for pre-reinforcement and thermoplastic resins, make fabrics from such filaments, and use this fabric as a forming material. As such a yarn, the following proposals are made.

(a) A preplastic yarn formed by twisting continuous fibers for reinforcement and thermoplastic resin fibers in a fibrous form.

(b) A preplastic yarn made by combing continuous fibers for reinforcement and thermoplastic resin fibers in a fibrous form.

(c) The pre-yarn made by adsorbing the thermoplastic resin powder on the connecting fiber for reinforcement by means of electricity, etc.

(d) A preformed bundle produced by passing continuous fibers for reinforcement through a thermoplastic resin melting tank.

(e) A thermoplastic resin is supplied at high pressure around the core containing continuous fibers for reinforcement and thermoplastic resin fibers to form a coated synthetic yarn while impregnating the core (JP-A-6-506643).

However, the conventional yarns shown in (a) to (e) above have the following problems, respectively.

The pre-plastic yarn of (a) needs the spinning process of thermoplastic material resin and the twisting process of reinforcing fiber, and the cost is relatively high. Moreover, in the processes such as this twisting process and subsequent processes such as spinning and thread making, the reinforcing fibers are easily damaged. Poor impregnation is prone to occur at the intersection of preplasticized yarns.

The pre-plastic yarn of (b) needs the spinning process of thermoplastic resin and the twisting process of reinforcing fiber, and the cost is relatively high. Moreover, in the processes of twisting, spinning, and thread making, the reinforcing fibers are greatly damaged.

(c) The pre-plastic yarn has uneven adsorption of tree powder, and it is difficult to control the amount of resin. In textile, thread making and other projects, the reinforcing fiber is greatly damaged.

The preplastic yarn of (d) lacks flexibility in the preplastic bundle, cannot be spun and threaded, and in addition, the productivity is also low.

The synthetic yarn of (e) requires a spinning process of thermoplastic resin and a spinning process of reinforcing fibers, which is expensive. Since a large amount of covering resin penetrates into the interior, it becomes hard and difficult to weave and thread.

The present invention has been developed in view of various problems in the past, and an object of the present invention is to provide a method for manufacturing resin-coated reinforcing fiber filaments. This method can easily produce filaments formed of reinforcing fibers and thermoplastic resins. Good productivity, easy to weave, thread, and flexible, can prevent damage to the reinforcing fiber in the process of weaving, thread, etc.

In order to solve the above problems, the inventors of the present invention conducted intensive research and found that the outer periphery of a reinforcing fiber bundle formed of a plurality of reinforcing continuous fibers is coated with a thermoplastic resin so that it adheres only to the fibers located on the outer periphery. , can form flexible resin-coated reinforcing fiber filaments almost without immersion into the interior, and this resin-coated reinforcing fiber filament can be easily processed into fabrics and boards, etc. At the same time, such fabrics and boards, as The forming material has very good properties, thus achieving the present invention.

That is, the resin-coated reinforcing fiber yarn of the present invention is characterized in that the resin-coated reinforcing fiber yarn used for manufacturing a fiber-reinforced thermoplastic resin molded article, the reinforcing fiber bundle formed of a plurality of continuous fibers for reinforcement, and the reinforcement The outer periphery of the fiber bundle is coated with a thermoplastic resin. The thermoplastic resin hardly penetrates into the interior of the above-mentioned reinforcing fiber bundle, but adheres to the continuous fibers located on the outer periphery, and the volume content of the continuous fiber for reinforcement is 40~ 60%.

As the reinforcing fiber used in the present invention, as long as the form is a continuous fiber, it may be a monofilament or a single strand. As the type, carbon fibers, inorganic fibers such as glass fibers and alumina fibers, and organic fibers such as aramid fibers can be used, without being strictly limited. A plurality of these reinforcing fibers are bundled and used in the form of a reinforcing fiber bundle. In the form of such a reinforcing fiber bundle, a plurality of continuous fibers may be formed into a bundle, or may be appropriately twisted to form a yarn. The fiber diameter and the number of fibers of the reinforcing fibers constituting the reinforcing fiber bundle can be determined according to the conditions required for forming materials such as fabrics and boards produced by coating the reinforcing fiber yarns with the resin. In order to protect the reinforcing fiber bundles as described later, they are bundled as much as possible in order to protect them by covering them with resin, and to minimize damages in subsequent processes. Specifically, when the reinforcing fibers are carbon fibers or glass fibers, the fiber diameter is 3 to 20 μm, preferably 5 to 10 μm, and the number of fibers is 2,000 to 17,000, preferably 5,000 to 15,000. In addition, for aramid fibers, the fiber diameter It is preferably 10 to 14 μm, and the number of fibers is preferably 600 to 5,000.

As thermoplastic resins used in the present invention, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6, nylon 66, and nylon 12, polypropylene, polyethylene, etc., can be used. , polycarbonate, polyaryl sulfone, polyether imine, polysubunit sulfite, polyether ether ketone, etc., are not strictly limited. In addition, several kinds of the above-mentioned thermoplastic resins may be used as a mixture, or a colorant, a filler, a flame retardant, and the like may be appropriately added to the above-mentioned thermoplastic resins for use.

In the resin-coated reinforcing fiber filaments of the present invention, the volume content of continuous fibers for reinforcement is between 40 and 60%, and therefore, the volume content of thermoplastic resin is also selected between 40 and 60%. Here, the volume content of thermoplastic resin is 40% or more. This is because if it is insufficient, coating is difficult, and the formed film is thin, and it is easy to peel off in the subsequent process, which may cause failure. In addition, when the volume content of the thermoplastic resin exceeds 60%, the resin component becomes too large, and the resin-coated reinforcing fiber becomes hard, making it difficult to process in a subsequent process. Furthermore, the range of the reinforcing fiber content is the same as the range of the reinforcing fiber content of the moldable article, so there is also an advantage that the molded article can be formed only by using the resin-coated reinforcing fiber filaments of the present invention.

In the resin-coated reinforcing fiber filaments of the present invention, the coated thermoplastic resin hardly penetrates into the interior of the reinforcing fiber bundle, but is in contact with the continuous fibers located on the outer periphery. In this way, since the thermoplastic resin does not impregnate the inside of the reinforcing fiber bundle, the fibers inside the reinforcing fiber bundle are not fixed to each other, so the overall flexibility can be maintained. Furthermore, since the coated thermoplastic resin is in contact with the continuous fibers located on the outer periphery of the reinforcing fiber bundle, the thermoplastic resin coating is not easily peeled off, thereby preventing the use of such resin-coated reinforcing fiber filaments in weaving and thread making. Failure may occur due to peeling of the thermoplastic resin coating in the post-process.

The present invention also provides a method for manufacturing the resin-coated reinforcing fiber having the above structure. That is, the method for producing resin-coated reinforcing fiber yarns according to the present invention is characterized in that the reinforcing fiber bundle formed by a plurality of reinforcing continuous fibers is arranged in a moving state to surround the reinforcing fiber bundle without contacting the reinforcing fiber bundle. The ring-shaped spout at the position extrudes the molten thermoplastic resin into a hollow cylinder, and under no pressure, makes the thermoplastic resin contact with the outer periphery of the above-mentioned reinforcing fiber bundle for coating.

Hereinafter, the production method of the present invention will be described in detail. Fig. 2 is a simplified side view of an embodiment of the used coating device for implementing the method of the present invention, Fig. 1 is a schematic cross-sectional view of the right-angle feed die of the coating device, and Fig. 3 is a schematic view of the spray resin part of the right-angle feed die Brief sectional view, Fig. 4 is a sectional view at A-A in Fig. 3 . 1 denotes a reinforcing fiber bundle formed from a plurality of continuous fibers for reinforcement, 2 denotes a feeder for supplying the reinforcing fiber bundle 1, 3 denotes a rotary extruder for extruding molten resin, and 4 denotes a process performed on the periphery of the reinforcing fiber bundle 1. Coated right-angle feed die head, 5 represents the resin-coated reinforcing fiber filaments, 6 represents the thermoplastic resin cooling tank, 7 represents the winding device.

The right-angle feed die 4 has a fiber hole 10 through which the reinforcing fiber bundle 1 passes at its center, a cylindrical passage 11 through which molten resin passes around it, and an annular discharge port 12 is formed at its lower end. The size of the hole for fibers is made such that the reinforcing fiber bundle 1 can pass through slowly. For example, when the circular cross-sectional diameter of the reinforcing fiber bundle 1 is set at 1 mm, the inner diameter of the fiber hole 10 is set at 2-4 mm. The discharge port 12 is spaced apart from the fiber hole 10 passing through the reinforcing fiber bundle 1 . Therefore, the molten resin 14 discharged from the discharge port 12 contacts the outer periphery of the reinforcing fiber bundle 1 without pressure. When the distance from the spout 12 of the fiber hole 10 is too large, it takes a certain amount of time for the resin 14 ejected from the spout 12 to contact the reinforcing fiber bundle 1 with a circular cross section, and the necessary In the case of adhesive force, it is usually selected below 2 mm, preferably 1 mm.

Next, a method for producing resin-coated reinforcing fibers using the above-mentioned apparatus will be described. At first, thermoplastic resin is packed in the funnel 3a of screw extruder 3, is heated and melted at cylinder part 3b place, is closed in the right angle feed die head 4 by screw, is sent into the right angle feed die head 4 The molten resin 14 passes through the cylindrical passage 11 and is discharged into a cylindrical shape from the annular discharge port 12 at the lower end. On the other hand, the reinforcing fiber bundle 1 is drawn out from the yarn feeder 2 and moves downward in the fiber hole 10 at the center of the right-angle feed die 4 . Therefore, the resin 14 discharged from the discharge port 12 is in a state of surrounding the moving reinforcing fiber bundle 1 . The resin 14 discharged from the discharge port 12 shrinks by surface gravity and cooling, and further shrinks radially by being pulled downward, contacts the outer periphery of the reinforcing fiber bundle 1, and adheres to the continuous fibers in this portion. Thus, the resin 14 is coated on the outer periphery of the reinforcing fiber bundle 1 . The resin-coated reinforcing fiber filaments 5 formed by such application are then passed through a thermoplastic resin cooling tank 6 , cooled, and finally wound up on a winding device 7 .

In the above coating operation, the thermoplastic resin is ejected from the discharge port 12, and comes into contact with the outer periphery of the reinforcing fiber bundle 1 in a pressure-releasing state, that is, in a non-pressurized state. Accordingly, the resin 14 in contact with the reinforcing fiber bundle 1 hardly penetrates between the continuous fibers inside. In this way, the thermoplastic resin coating is bonded only to the continuous fibers located on the outer periphery of the reinforcing fiber bundle 1, thereby producing a resin-coated reinforcing fiber filament of this structure. Here, in order to ensure that the continuous fibers positioned at the outer periphery of the reinforcing fiber bundle 1 and the thermoplastic resin coating surrounding it can be well bonded, it is preferable to make the molten resin 14 ejected from the ejection port 12 not completely cooled and solidified. To be in contact with the reinforcing fiber bundle 1, it is preferable for the discharged molten resin 14 to be in contact with the reinforcing fiber bundle 1 between 5 and 30 mm below the discharge port 12. As the discharge temperature of the thermoplastic resin, it is preferable to adopt a temperature 30-60° C. higher than the melting point of the thermoplastic resin, and the viscosity of the molten resin at this time is preferably lower than 10,000 poise.

The present invention also provides a molding material for producing a fiber-reinforced thermoplastic resin molded article using the above-mentioned resin-coated reinforcing fiber yarn of the present invention. The molding material of the present invention will be explained below. A molding material according to an aspect of the present invention is a fabric woven using the above-mentioned resin-coated reinforcing fiber yarn. this fabric. The above-mentioned resin-coated reinforcing fiber yarns are used for both the warp and weft yarns, or the above-mentioned resin-coated reinforcing fiber yarns may be used for part of the warp and weft yarns, and the thermoplastic resin used for the resin-coated reinforcing fiber yarns may be used for the rest. and homogeneous thermoplastic resin fiber filaments. In the latter case, by adjusting the proportion of thermoplastic resin fiber filaments woven into the fabric, the reinforcing fiber content of the molded body obtained from the fabric can be adjusted.

When using the resin-coated reinforcing fiber filaments and the thermoplastic resin fiber filaments to weave the fabric, the arrangement of both is arbitrary, for example, the following combinations can be used.

① Both the warp and the weft use resin-coated reinforcing fibers and thermoplastic resin fibers.

②Warp and weft, only one side uses resin-coated reinforcing fiber yarn or thermoplastic resin fiber yarn, and the other uses resin-coated reinforcing fiber yarn.

③ One of the warp and weft uses resin-coated reinforcing fiber and thermoplastic resin fiber, and the other uses only thermoplastic resin fiber.

④ Only one of the warp and weft uses resin-coated reinforcing fibers, and the other uses only thermoplastic resin fibers.

These combinations are appropriately selected according to the properties of the molded article to be obtained. For example, in the combination of ① and ②, since the reinforcing fibers are arranged on both the warp and weft, a non-directional reinforced molded body can be obtained. In addition, in the combination of ③ and ④, since the reinforcing fibers are arranged only in one side of the warp or weft, it is possible to obtain a molded body reinforced only in one direction. In addition, even in the combination of ③ and ④, when the fabric is laminated, it is possible to obtain a non-directionally reinforced molded product by utilizing the direction crossing of the reinforcing fibers to laminate.

The weaving structure of the fabric used in the present invention is not particularly limited, and may be plain weave, twill, etc., and weaving is usually performed by a weaving machine as in the past. In this weaving process, the warp and weft are bent and kneaded. However, since the resin-coated reinforcing fiber filaments of the present invention have moderate flexibility, they will not be damaged even if they are bent. In addition, the reinforcing fiber bundles that are easily damaged by rubbing are covered with a thermoplastic resin coating. The reinforcing fibers cannot be damaged, nor can they produce burrs, etc. Since this thermoplastic resin coating is bonded to the continuous fibers at the periphery of the reinforcing fiber bundle, peeling is unlikely to occur. The fabric thus obtained has no damage to the reinforcing fibers constituting it. It also has soft properties.

Next, a forming method using this fabric will be described. Depending on the thickness of the desired molded object, it is sufficient to stack several fabrics and place them in the mold. This fabric is suitable not only for flat shapes but also for curved surfaces due to its softness and good formability. When the fabric is placed in the mold, in order to adjust the content of the reinforcing fiber in the molded body. A resin film can be placed between the fabrics. In addition, in order to ensure the necessary strength and rigidity, a fabric composed of only reinforcing fiber filaments, and a preform material in which reinforcing fibers are fused and impregnated with resin can be placed. However, since these resin films and preforms have poor formability, it is better to use less. Furthermore, fabrics made of only reinforcing fibers have poor impregnation properties, so it is better to use less. After being placed in the mold, pressurization and heat treatment are carried out as in the past. The pressure is 5-20Kg/cm ² , and the temperature used is appropriately 30-50°C higher than the melting point of the resin. According to this, the thermoplastic resin is melted and impregnated between the reinforcing fibers to form a substrate, and then cooled and solidified to obtain a fiber-reinforced thermoplastic resin molded body.

In the resin-coated reinforcing fiber filaments, the outer periphery of the reinforcing fiber bundle is surrounded by a thermoplastic resin. Therefore, when impregnating with pressure and heating, the distance that the molten resin flows is short, thereby obtaining reliable impregnation. Also, even at intersections of reinforcing fibers that are difficult to impregnate, since the coating resin exists between the reinforcing fibers, poor impregnation does not occur at this portion. In this way, the obtained molded body has good impregnation properties, almost no voids, and very good flexural strength.

Another aspect of the molding material of the present invention is a grid plate made of the above-mentioned resin-coated reinforcing fiber filaments. The grid plate is formed by arranging several wires in a helical shape in the S direction (hereinafter referred to as the S direction wires), and in the Z direction intersecting with it, arranging several wires in a helical shape (hereinafter referred to as the Z direction wires), but in In the grid panel of the present invention, both the S-direction thread and the Z-direction thread can use the above-mentioned resin-coated reinforcing fiber thread. Some of the S-direction yarns and the Z-direction yarns may use the above-mentioned resin-coated reinforcing fiber yarns, and the remaining part may use the thermoplastic resin and homogeneous thermoplastic resin fiber yarns used for the resin-coated reinforcing fiber yarns. The latter can be adjusted by adjusting the proportion of thermoplastic resin fiber filaments added to the grid board to adjust the content of the reinforcing fiber formed by using the grid board.

When the resin-coated reinforcing fiber filaments and thermoplastic resin fiber filaments are used to form the wire grid panel, the arrangement of the two is optional. For example, the following combinations can be used.

⑤Resin-coated reinforcing fiber yarns and thermoplastic resin fiber yarns are used for both S-direction yarns and Z-direction yarns.

⑥ One of the S-direction yarns and the Z-direction yarns uses resin-coated reinforcing fiber yarns and thermoplastic resin fiber yarns, while the other uses only resin-coated reinforcing fiber yarns.

⑦ One of the S-direction yarns and the Z-direction yarns uses resin-coated reinforcing fiber yarns and thermoplastic resin fiber systems, while the other uses only thermoplastic resin fiber yarns.

⑧ One of the S-direction yarns and the Z-direction yarns uses only resin-coated reinforcing fiber yarns, while the other uses only thermoplastic resin fiber yarns.

These combinations can be appropriately selected according to the properties of the desired molded article. For example, in the combination of ⑤ and ⑥, since both the S-direction yarn and the Z-direction yarn are arranged with reinforcing fibers, a non-directional reinforced molded product can be obtained. In addition, in the combination of ⑦ and ⑧, since only one of the S-direction yarn and the Z-direction yarn is arranged with reinforcing fibers, only a molded body reinforced in one direction can be obtained. In addition, even in the combination of ⑦ and ⑧, when laminating such a lattice board, cross-lamination is carried out in the direction of the reinforcing fibers, and a molded body with non-directional reinforcement can still be obtained.

The wire making of the above-mentioned grid board does not use a special device, and a general wire making machine can be used. That is, the resin-coated reinforcing fiber filaments pre-wound on the wire-making tube (and the thermoplastic resin fiber pre-wound on the wire-making tube) are installed on the right (rotary) side of the wire-making machine, On the cannula on the left (rotary) side, use a wire machine to make it into a grid plate. At this time, the resin-coated reinforcing fiber yarn is kneaded while being bent. As in the case of the above-mentioned weaving, the resin-coated reinforcing fiber yarn of the present invention has moderate flexibility, so it will not be damaged even if it is bent. There will be no damage to the fiber, such as burrs. Furthermore, since this thermoplastic resin coating film adheres to the continuous fibers at the outer periphery of the reinforcing fiber bundle, peeling does not occur. The lattice panels thus obtained are free from damage to the reinforcing fibers constituting them and have soft properties.

Since the grid plate of the present invention is formed into a cylindrical shape, it is suitable for processing into a molded body of a fiber-reinforced thermoplastic resin pipe. A method of forming a fiber-reinforced thermoplastic resin pipe (FRTP pipe) using this grid plate will be described below. First, according to the required thickness of the molded body, several grid plates are wrapped on the rod core. At this time, since the grating has flexibility, it is easy to handle. In order to adjust the reinforcing fiber content in the molded body when the gratings are installed on the core, resin tubes may be arranged between the layers of the gratings. In addition, in order to ensure the necessary strength and rigidity, resin-impregnated preformed materials and reinforcing fiber fabrics incorporating reinforcing fibers such as 0, 90°, etc. can also be placed between the lattice board layers. However, since these resin films and preforms have poor formability, it is better to use less. Furthermore, fabrics formed of reinforcing fibers are preferably used sparingly due to their poor impregnation properties.

Next, pull out the rod core, and install a tube for internal pressure such as silicon. Then, such an installation is put into a predetermined mold, and a gas such as nitrogen or air is injected into the internal pressure tube under pressure while heating. The pressing pressure is about 5-20Kg/cm ² , and the operating temperature is suitably higher than the melting point of the resin by 30-50°C. By heating and pressurizing, the thermoplastic resin is melted and impregnated between reinforcing fibers to form a matrix. Then, the mold is cooled to solidify the thermoplastic resin matrix in a molten state, and the molded body is taken out from the mold. Through the above steps, a thermoplastic resin hollow molded body reinforced with continuous fibers is obtained. The obtained molded body has almost no voids, and exhibits an effect superior to that of fiber-reinforced flexural strength and torsional strength.

Although the resin-coated reinforcing fiber filament of the present invention is constituted by coating a thermoplastic resin on a reinforcing fiber bundle formed of a plurality of continuous fibers, this thermoplastic resin can hardly be impregnated in the reinforcing fiber bundle. Even if the resin content is as high as 40 to 60% inside, it doesn’t matter, it still has flexibility, and the outer peripheral thermoplastic resin coating protects the internal reinforcing fiber bundles, so in the process of weaving, thread making, etc., prevent The reinforcing fibers are damaged. Furthermore, the thermoplastic resin coating is adhered to the continuous fibers at the outer periphery of the reinforcing fiber bundle and has an appropriate thickness so that it will not be peeled off during the processes of spinning, thread making, and the like. Therefore, as a molding material for fabricating a fiber-reinforced thermoplastic resin molded body, it is preferable to use its fabric or a lattice board as a material.

The method of the present invention is to extrude the thermoplastic resin surrounding the reinforcing fiber bundle in a hollow cylindrical shape under a moving state of the reinforcing fiber bundle formed by a plurality of continuous fibers for reinforcement, and to extrude the above-mentioned Since the outer periphery of the reinforcing fiber bundle is in contact, the resin-coated reinforcing fiber yarn of the present invention is produced in which the resin is not impregnated inside the reinforcing fiber bundle but adheres to the continuous fibers on the outer periphery. At this time, after the thermoplastic resin is extruded in a molten state, since it is in contact with the periphery of the reinforcing fiber bundle without pressure, the processing speed (moving speed of the reinforcing fiber bundle) can be very high, for example, it can be 200 m/min. (m/min). For this reason, production efficiency can be improved.

The molding material formed from the fabric woven by using the above-mentioned resin-coated reinforcing fiber filaments has softness due to the use of soft resin-coated reinforcing fiber filaments, so it has good formability and is suitable for processing into molded objects with curved surfaces. , and at the same time, the operability in layering and forming is also good. At the same time, since the thermoplastic resin is evenly coated on the outer periphery of the reinforcing fiber bundle, the impregnation during forming is very good, even at the intersection of the reinforcing fibers in the fabric, the impregnation is also very good, and the dispersion of the reinforcing fibers Also very good. As a result, forming can be performed in a shorter time and with lower pressure.

Like the case of fabrics, the molded material formed from the grid plate processed by using the above-mentioned resin-coated reinforcing fiber yarns has flexibility due to the use of soft resin-coated reinforcing fiber yarns, so the formability is very good. Well, the operability at the time of lamination and shaping is also good. Moreover, since the thermoplastic resin is evenly coated on the outer periphery of the reinforcing fiber bundle, the impregnation during molding is very good, and even at the intersecting points of the reinforcing fibers in the fabric, the impregnation is also good, and the dispersion of the reinforcing fibers also good. For this reason, forming can be carried out in a short time and under low pressure. Since such a grid plate has a cylindrical shape, it is suitable for processing into a tubular molded body of fiber-reinforced thermoplastic resin.

Example 1

Under the following conditions, resin-coated reinforcing fiber filaments were produced, and the following results were obtained.

(1) Materials used

  Reinforced fiber bundle: carbon fiber

HTA-6KCF (manufactured by Toho レ-ヨン Co., Ltd.)

                                          6000

            Monofilament diameter 7μm

  Thermoplastic resin: polyamide

           PA6 (manufactured by Ube Industries, Ltd.)

(2) Coating conditions

 Using device: the structure shown in Figure 1-4

The inner diameter of the fiber hole 10: 3.5mm

The outer diameter of the spout 12: 7mm inner diameter: 5.5mm

  Right-angle feeding die head temperature: 270°C

Barrel temperature of extruder 3: 250°C

 Output of thermoplastic resin: 46 g/min

  Winding speed: 200 m/min

(3) Results

A resin-coated reinforcing fiber filament having thermoplastic resin coating on the outer periphery of the reinforcing fiber bundle is obtained. The reinforcing fiber volume content of the obtained resin-coated reinforcing fiber filaments was 54%. When the resin-coated reinforcing fiber filaments were cut and the cross-section was observed with an electron microscope, a plastic resin coating was formed to surround the reinforcing fibers. It is a continuous fiber bonded to the periphery of the reinforcing fiber. At the same time, impregnation of the resin into the inside of the reinforcing fibers was not found. Furthermore, when the plastic resin coating of the mat was peeled off and the internal reinforcing fibers were inspected, no damage was found to the internal reinforcing fibers. Therefore, it was concluded that the reinforcing fibers were not damaged during the coating process.

The obtained resin-coated reinforcing fiber filaments were soft, and no damage occurred in the weaving test, and weaving was feasible.

Example 2

Resin-coated reinforcing fiber filaments were produced under the following conditions, and the results obtained are as follows.

(1) Materials used

  Reinforced fiber bundle: carbon fiber

HTA-6KCF (manufactured by Toho レ-ヨン Co., Ltd.)

                                      6000

        Monofilament diameter 7μm

  Thermoplastic resin: polyphenylene sulfite

PPS (manufactured by Dainippon Inki Co., Ltd.)

(2) Coating conditions

 Using device: the structure shown in Figure 1-4

The inner diameter of the fiber hole 10: 3.5mm

The outer diameter of the spout 12: 7mm. Inner diameter: 5.5mm

  Right Angle Feed Die Temperature: 320°C

Barrel temperature of extruder 3: 290°C

 Output of thermoplastic resin: 46g/min

  Winding speed: 200m/min

(3) Results

A resin-coated reinforcing fiber filament having thermoplastic resin coating on the outer periphery of the reinforcing fiber bundle is obtained. The reinforcing fiber volume content of the obtained resin-coated reinforcing fiber filaments was 54%. This resin-coated reinforcing fiber yarn also had the same characteristics as in Example 1.

Example 3

The following results were obtained by producing resin-coated reinforcing fiber filaments under the following conditions.

(1) Materials used

Reinforcement Fiber Bundle: Carbon Fiber

       HTA-6KCF (manufactured by Toho レ-ヨン Co., Ltd.)

                                          6000

              Monofilament diameter 7μm

Thermoplastic resin: Polyamide

       PA6 (manufactured by Ube Industries, Ltd.)

(2) Coating conditions

 Using device: the structure shown in Figure 1-4

The inner diameter of the fiber hole 10: 3.5mm

The outer diameter of the spout 12: 7mm. Inner diameter: 5.5mm

  Right Angle Feed Die Temperature: 280°C

Barrel temperature of extruder 3: 250°C

 Output of thermoplastic resin: 30g/min

  Winding speed: 130m/min

(3) Results

A resin-coated reinforcing fiber filament having thermoplastic resin coating on the outer periphery of the reinforcing fiber bundle is obtained. The resulting resin-coated reinforcing fiber yarn had a reinforcing fiber volume content of 54% and this resin-coated reinforcing fiber yarn also had the same characteristics as in Example 1.

Example 4

Resin-coated reinforcing fiber yarns were produced under the following conditions, and the following results were obtained.

(1) Materials used

Reinforcement Fiber Bundle: Carbon Fiber

       HTA-12KCF (manufactured by Toho レ-ヨン Co., Ltd.)

                                                                   

              Monofilament diameter 7μm

Thermoplastic resin: Polyamide

        PA6 (manufactured by Zibu Kosan Co., Ltd.)

(2) Coating conditions

 Using device: the structure shown in Figure 1-4

The inner diameter of the fiber hole 10: 5mm

The outer diameter of the spout 12: 9mm. Inner diameter: 7mm

  Right-angle feeding die head temperature: 270°C

Barrel temperature of extruder 3: 250°C

 Output of thermoplastic resin: 30g/min

  Winding speed: 65m/min

(3) Results

A resin-coated reinforcing fiber filament having thermoplastic resin coating on the outer periphery of the reinforcing fiber bundle is obtained. The resulting resin-coated reinforcing fiber yarn had a reinforcing fiber volume content of 54% and this resin-coated reinforcing fiber yarn also had the same characteristics as in Example 1.

Example 5

Using the resin-coated reinforcing fiber filaments of Example 3, fabrics were woven under the following conditions.

Textile form: plain weave

Weaving density: The fabric obtained by warp 10 threads/25mm and weft 10 threads/25mm was soft, and no damage was found in the diameter yarn and the weft yarn. Using this fabric, it was processed into a flat panel under the following conditions.

Lamination composition: 8 layers (ply)

Forming conditions: 270° C., 10 Kgf/cm ² , 10 minutes, and a molded body having a thickness of 2.1 mm was obtained by such forming. Table 1 shows the results of mechanical properties measurement on this molded body.

Comparative example 1

Fabrics formed of reinforcing fiber bundles and thermoplastic resin films of the following specifications were prepared.

Reinforced fiber fabric.

Use fiber: carbon fiber

      T-3006KCF fabric (manufactured by Toray Co., Ltd.)

                            6000

      Monofilament diameter 7μm

     Textile Form: Plain Weave

Textile density: diameter 10/25mm, weft 10/25mm

Thermoplastic resin: polyamide

PA6 film thickness 60μm (manufactured by Yunichika Co., Ltd.)

Using this reinforcing fiber fabric and thermoplastic resin film, it was processed into a flat plate under the following conditions.

Laminated structure: the surface is formed by PA6 film, PA6 film and reinforced fiber fabric are cross-laminated with each other, and the reinforced fiber fabric has 8 layers.

Forming conditions: 270°C, 10Kgf/cm ² , 10 minutes

By molding in this way, a molded body having a thickness of 2.2 mm was obtained. Table 1 shows the measurement results of the mechanical properties of this molded body. The bending strength was measured according to JISK7203, the tool impact value was measured according to TISK7111, and the porosity was measured according to JISK7053.

Table 1 Example 5 Comparative example 1 Reinforced Fiber Volume Content (%) Bending Strength (Kgf/mm ² ) Exact Impact Value (Kgf·cm/cm ² ) Void Ratio (%) 5470921 54123821

It is apparent from Table 1 that the molded article obtained in Example 5 has considerably superior characteristics to the molded article of Comparative Example 1 obtained from the conventional reinforcing fiber fabric.

Example 6

The resin of Example 4 was used to coat the reinforcing fiber filaments, and wire grid panels were produced under the following conditions.

Number of bobbins: 24 dozen

Angle: 30°

Grid plate diameter: 18mm

The obtained grid panel was soft, and no damage to the resin-coated reinforcing fiber filaments was found. Using this grid plate, it was processed into a tube under the following conditions.

Lamination composition: 3 layers (ply)

Forming conditions: 260°C, internal pressure 10Kgf/cm ² , 20 minutes, cooling 15°C/min, demoulding below 80°C.

The obtained FRTP pipe had an outer diameter of 20 mm, a thickness of 1.2 mm, and a volume content of reinforcing fibers of 55%. Table 2 shows the measurement results of its mechanical properties.

Comparative example 2

According to the following conditions, a 12KCF/PA6 interwoven grid plate is made, and the FRTP pipe is made by internal pressure forming method.

(1) Materials used

Reinforced fiber bundle: carbon fiber

HTA-12KCF (manufactured by Toho Re-ヨン Co., Ltd.)

        Number of single wires: 12,000

  Monofilament diameter: 7μm

Thermoplastic resin fiber: nylon fiber

           PA6 (manufactured by Ube Industries, Ltd.)

                                                           

            Monofilament diameter 82μm

                                                    

(2) Weaving conditions

Number of bobbins: 48 dozen

Angle: 30°

Grating Diameter: 18mm

Place the left-handed and right-handed carbon fiber and nylon fiber tubes at intervals, and arrange the reinforcing fibers in the same amount in the direction of crossing each other to make an interwoven grid plate

(3) Internal pressure forming

Using the obtained grid plate, FRTP-shaped pipes were produced under the following conditions.

Laminated composition: 3 layers

Forming conditions: 260°C, internal pressure 8kgf/cm ² , 10 minutes, cooling 15°C/min, demoulding below 80°C

The obtained FRTP pipe had an outer diameter of 20 mm, a thickness of 1.2 mm, and a volume content of reinforcing fibers of 55%. Table 2 shows the measurement results of its mechanical properties.

Comparative example 3

According to the following conditions, 12KCF/PA6 1-direction grid plate was produced, and it was processed into FRTP pipe by internal pressure forming method.

(1) Use material to reinforce fiber bundle: carbon fiber

HTA-12KCF (manufactured by Toho レ-ヨン Co., Ltd.)

         Number of single filaments: 12,000

  Monofilament diameter: 7μm

 Thermoplastic resin fiber: nylon fiber

        PA6 (manufactured by Ube Industries, Ltd.)

          Number of single filaments: 72

  Monofilament diameter: 82μm

        Yarn Count: 460TEX

(2) Textile conditions

Number of bobbins: 32 dozen

Angle: 30°

Grating Diameter: 18mm

Place a carbon fiber wire tube on the left-handed intubation tube, and place a nylon fiber wire-making tube on the right-handed intubation tube to make a reinforced grid plate in the Z direction. Place a carbon fiber wire tube on the right-handed cannula, and place a nylon-made wire tube on the left-handed cannula to make a grid plate reinforced in the S direction.

(3) Internal pressure forming

Using the obtained grid plate, FRTP formed pipes were produced under the following conditions.

Lamination composition: 4 layers, the Z-direction reinforced lattice board and the S-direction reinforced lattice board are alternately laminated to make 4 layers.

Forming conditions: 260°C, internal pressure 8Kgf/cm ² , 10 minutes, cooling 15°C/min, demoulding below 80°C.

The obtained FRTP pipe has an outer diameter of 20 mm, a thickness of 1.1 mm, and a volume content rate of reinforcing fibers of 55%. Its mechanical properties are listed in Table 2. The flexural strength was measured according to JIS K7203, and the porosity was measured according to JIS K7053. Bending strength (kgf/mm ² ) Porosity (%) Example 6 Comparative Example 2 Comparative Example 3 1107590 2.58.55.0

It is clear from Table 2 that the molded body obtained in this Example 6 has more excellent characteristics than those obtained in Comparative Examples 2 and 3 obtained by using the conventional reinforced fiber lattice board.

As explained above, the resin-coated reinforcing fiber yarn of the present invention is coated with a thermoplastic resin to obtain a reinforcing fiber bundle formed of a plurality of continuous fibers, and has moderate flexibility, so it can be used in spinning, thread making and other processes. It does not cause damage and is suitable for use as a fabric or grid board material used as a molding material for making fiber-reinforced thermoplastic resin moldings. Moreover, when molding, the resin has good impregnation with reinforcing fibers, and its effect can be processed into high-quality molding. body. Furthermore, this resin-coated reinforcing fiber filament, due to the thermoplastic resin, is in an integrated covering form for the reinforcing fiber. Compared with the preformed yarn formed by twisting or combing the fiber compounding reinforcing fiber, the manufacturing process is simple. The cost is cheap. Furthermore, since the reinforcing fibers are covered and protected with thermoplastic resin, there is no trouble in the subsequent process. Thereby, many single fibers can be used to form the reinforcing fiber bundle, and there are effects such as good productivity.

The molding material of the present invention, which is formed by weaving the above-mentioned resin-coated reinforcing fiber filaments, has flexibility due to the use of soft resin-coated reinforcing fiber filaments, so it has good formability and is suitable for processing into shapes with curved surfaces. At the same time, the operability of layering and forming is very good. And because the thermoplastic resin is evenly coated on the outer periphery of the reinforcing fiber bundle, the impregnation during molding is good, even at the intersecting points of the reinforcing fibers in the fabric, the impregnation is also very good, and the dispersion of the reinforcing fibers is also good. . Thus, molding can be performed under low pressure in a short period of time, and a molded body with low porosity and high reinforcing effect can be produced.

The molding material of the present invention, which is formed by covering the grid plate formed by the above-mentioned resin-coated reinforcing fiber yarn, is also the same as the case of the fabric. Since the soft resin-coated reinforcing fiber yarn is used, it has flexibility. Good properties, good operability when layering and shaping. Since the thermoplastic resin is uniformly coated on the outer periphery of the reinforcing fiber bundle, impregnation of the formed pair is excellent. Therefore, it can be formed and processed under low pressure in a short period of time. A molded body with low porosity and high reinforcing effect can be produced. The effect is very suitable for processing into a fiber-reinforced thermoplastic resin tubular molded body.

The method of the present invention is to use a plurality of reinforcing fiber bundles formed by continuous fibers for reinforcement, and extrude the thermoplastic resin surrounding the reinforcing fiber bundles into a hollow cylinder in a moving state. The outer periphery of the bundle is in contact with each other to manufacture the resin-coated reinforcing fiber yarn of the present invention, so that the resin is not impregnated into the interior of the reinforcing fiber bundle, but is bonded to the continuous fiber on the outer periphery. At this time, the melted thermoplastic resin is in contact with the outer periphery of the reinforcing fiber bundle in a non-pressurized state, so that the processing speed can be increased and the productivity can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a schematic sectional view of an example of a right-angle feed die of a coating apparatus used in the production method of the present invention.

Fig. 2 shows a schematic side view of the coating device.

Fig. 3 is a schematic sectional view of a resin discharge portion of a right-angle feed die.

FIG. 4 is a cross-sectional view along line A-A of FIG. 3 .

The symbols in the figure are:

1 Reinforced fiber bundle 2 Wire feeding device

3 screw extruder 4 right angle feed die head

5 Resin-coated reinforced fiber filaments 6 Thermoplastic resin cooling tank

7 Winding device 10 Fiber hole

11 Cylindrical channel 12 Spout port

14 resin

Claims (1)

1. A manufacturing method for manufacturing resin-coated reinforcing fiber filaments, characterized in that the reinforcing fiber bundle formed by a plurality of reinforcing peripheral continuous fibers is in a moving state, and is arranged to surround the reinforcing fiber bundle without contacting the reinforcing fiber bundle. The ring-shaped nozzle at the position of the fiber bundle extrudes the molten thermoplastic resin into a hollow cylinder, and applies the thermoplastic resin in contact with the outer periphery of the above-mentioned reinforcing fiber bundle under no pressure. .

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