JPH08336879A - Resin-coated reinforcing fiber yarn, molding material and manufacture thereof - Google Patents

Abstract

PURPOSE: To provide a reinforcing fiber yarn capable of being simply manufactured by yarns made of reinforcing fiber and thermoplastic resin with excellent productivity and having excellent weaving property and stranding property, a method for manufacturing the same, and a molding material using the reinforcing fiber yarn and having excellent shaping properties at the time of molding and being scarcely impregnated. CONSTITUTION: Reinforcing fiber yarn covered on the outer periphery of a fiber bundle so formed of many reinforcing continuous fibers with thermoplastic resin as not to almost impregnate within the fiber bundle and thermoplastic resin 14 melted on the periphery of the bundle 1 are extruded in a cylindrical state on the outer periphery of the bundle formed of may reinforcing continuous fibers, and brought into contact with the outer periphery of the bundle 1 in a zero-pressure state.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated reinforcing fiber yarn used for molding a thermoplastic resin molded product reinforced with continuous fibers, a molding material using the resin-coated reinforcing fiber yarn,
And a method for producing the resin-coated reinforcing fiber yarn.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resin moldings reinforced with continuous fibers have been widely used because of their great reinforcing effect. In order to form such a continuous fiber-reinforced thermoplastic resin molded body, usually, a method in which sheets made by impregnating a thermoplastic resin into reinforcing fibers are laminated, heated and pressed, and molded, are formed by reinforcing fiber yarns. And the thermoplastic resin film are alternately laminated and heated and pressed to form, or a woven woven fabric of reinforcing fiber yarn and thermoplastic resin fiber yarn is laminated and heated and pressed to form. Has been done.
However, when a film or a sheet is used as the laminated material, there is a problem that the shapeability when molding a three-dimensional shape is poor. Further, when a woven fabric is used, there is a problem that the resin impregnating property with respect to the reinforcing fiber is poor, and particularly, the resin impregnating property is poor at the intersection of the reinforcing fibers in the woven fabric. Furthermore, when weaving the reinforcing fiber yarns, the fibers are easily separated and damaged, so that the number of single fibers constituting one reinforcing fiber yarn cannot be increased very much (for example, in the case of glass fiber having a single yarn diameter of 7 μm, However, it was not possible to increase productivity by increasing the number of single fibers.

Therefore, in order to improve the resin impregnation property, a yarn (tow, containing a continuous fiber for reinforcement and a thermoplastic resin in advance).
It has been proposed to prepare a yarn, etc.), make a woven fabric from the yarn, and use the woven fabric as a molding material, and the following yarns have been proposed. (A) A prepreg yarn made by twisting reinforcing continuous fibers and thermoplastic resin fibers in a fiber state. (B) A prepreg yarn produced by commingling continuous reinforcing fibers and thermoplastic resin fibers in a fiber state. (C) A prepreg yarn produced by adsorbing a thermoplastic resin powder on a reinforcing continuous fiber by using static electricity or the like. (D) A prepreg tow produced by passing continuous reinforcing fibers through a molten bath of thermoplastic resin. (E) Synthetic yarn in which molten thermoplastic resin is supplied to the outer periphery of a core containing continuous reinforcing fibers and thermoplastic resin fibers at a high pressure to impregnate the inside of the core and coat the same (see Japanese Patent Publication No. 6-5066).
43 publication).

[0004]

However, the above (a)-
The conventional yarn shown in (e) has the following problems. The prepreg yarn of (a) requires a spinning step of a thermoplastic resin and a twisting step with a reinforcing fiber, resulting in high cost. In addition, the reinforcing fiber is damaged in the ply-twisting step and the subsequent steps such as weaving and stringing. Impregnation is likely to occur at the intersection of prepreg yarns. The prepreg yarn of (b) requires a spinning step of the thermoplastic resin and a commingle step with the reinforcing fiber, which results in high cost. In addition, the damage to the reinforcing fiber is large in the steps such as combing, weaving, and stringing. In the prepreg yarn of (c),
Adsorption of resin powder is non-uniform, it is difficult to control the amount of resin, and damage to the reinforcing fiber is large in the processes such as weaving and stringing. In the prepreg tow of (d), the prepreg tow does not have flexibility and cannot be woven or stringed. Also, productivity is low. The synthetic yarn (e) requires a spinning process of a thermoplastic resin and a yarn-forming process with a reinforcing fiber, resulting in high cost. It is hard because the coating resin is impregnated into the interior, making it difficult to weave or string.

The present invention has been made in view of the above conventional problems, and is a thread made of a reinforcing fiber and a thermoplastic resin, which can be manufactured simply and with high productivity, and can be easily woven and braided. An object of the present invention is to provide a yarn having flexibility and capable of preventing damage to a reinforcing fiber in a process such as weaving and stringing, and a manufacturing method thereof. Another object of the present invention is to provide a molding material having good shapeability during molding and less likely to cause impregnation failure by using the yarn.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that only the fibers located on the outer circumference of a reinforcing fiber bundle formed of a large number of continuous reinforcing fibers are used. By coating with a thermoplastic resin so as to adhere and hardly impregnate the inside, a resin-coated reinforcing fiber yarn having appropriate flexibility can be formed, and this resin-coated reinforcing fiber yarn can be easily applied to fabrics, blades, etc. The present invention has been accomplished by finding that the woven fabric and the blade are processable and have favorable characteristics as a molding material.

That is, the present invention relates to a resin-coated reinforcing fiber yarn used for producing a fiber-reinforced thermoplastic resin molded article, which is a reinforcing fiber bundle formed of a large number of reinforcing continuous fibers, and a reinforcement thereof. It is composed of a thermoplastic resin coated on the outer periphery of the fiber bundle, the thermoplastic resin is almost not impregnated inside the reinforcing fiber bundle, and is bonded to continuous fibers located on the outer periphery. The resin coated reinforcing fiber yarn is characterized by having a volume content of 40 to 60%.

The reinforcing fiber used in the present invention may be in the form of filament yarn or strand as long as it is a continuous fiber. As the type, inorganic fibers such as carbon fibers, glass fibers, and alumina fibers, and organic fibers such as aramid fibers are used, but are not limited thereto. These reinforcing fibers are used in the state of a reinforcing fiber bundle formed by bundling a large number of them. The form of the reinforcing fiber bundle may be a tow formed by simply bundling a large number of continuous fibers, or a yarn in which an appropriate twist is added. The fiber diameter of the reinforcing fibers constituting the reinforcing fiber bundle, the number of fibers, etc., is a woven fabric manufactured from this resin-coated reinforcing fiber yarn,
It is determined according to the conditions required for the molding material such as the blade, but since the reinforcing fiber bundle is protected by the resin coating as will be described later, it is less likely to be scattered or damaged in the subsequent process, Therefore, it is possible to increase the number of bundles. Specifically, when the reinforcing fiber is carbon fiber or glass fiber, the fiber diameter is 3 to 20 μm, preferably 5
-10 μm, the number of fibers is 2,000 to 17,000, preferably 5,000 to 15,000, and in the case of aramid fibers, the fiber diameter is 10 to 14 μm.
The number of fibers is preferably about 600 to 5000.

Examples of the thermoplastic resin used in the present invention include polyesters such as polyethylene terephthalate and polybutylene terephthalate, nylon 6, nylon 6 and the like.
6, polyamide such as nylon 12, polypropylene,
Polyethylene, polycarbonate, polyallyl sulfone, polyether imide, polyphenylene sulfide, polyether ether ketone, etc. are used, but not limited thereto. It is also possible to mix and use a plurality of types of the above-mentioned thermoplastic resins, and it is also possible to use the above-mentioned thermoplastic resins by adding an appropriate amount of a colorant, a filler, a flame retardant or the like.

In the resin-coated reinforcing fiber yarn of the present invention, the volume content of the reinforcing continuous fibers is 40 to 60%, and therefore,
The volume content of the thermoplastic resin is also selected to be 40 to 60%. Here, the volume content of the thermoplastic resin is set to 40% or more because if it is less than that, the coating is difficult, and the formed coating film is thin and may be peeled off in a later step to cause a trouble. . On the contrary, when the volume content of the thermoplastic resin exceeds 60%, the resin content becomes too large and the resin-coated reinforcing fiber yarn becomes hard, which makes it difficult to process in the subsequent step. Further, the range of the content rate of the reinforcing fiber matches the range of the content rate of the reinforcing fiber desired for the molded article, and therefore, there is an advantage that the molded article can be formed only by the resin-coated reinforcing fiber yarn of the present invention. Have

In the resin-coated reinforcing fiber yarn of the present invention, the coated thermoplastic resin does not substantially impregnate the inside of the reinforcing fiber bundle and is bonded to the continuous fibers located on the outer periphery. Since the thermoplastic resin is not impregnated into the reinforcing fiber bundle as described above, the fibers are not fixed to each other inside the reinforcing fiber bundle and the overall flexibility is maintained. Further, since the coated thermoplastic resin is adhered to the continuous fibers located on the outer periphery of the reinforcing fiber bundle, the thermoplastic resin coating is difficult to peel off, and weaving using this resin-coated reinforcing fiber yarn, after the braiding, etc. It is possible to prevent the thermoplastic resin film from peeling off and causing trouble in the process.

The present invention also provides a method for producing the resin-coated reinforcing fiber yarn having the above structure. That is, the present invention, in the state of running a reinforcing fiber bundle formed of a large number of reinforcing continuous fibers, to surround the reinforcing fiber bundle, and an annular shape arranged at a position not contacting the reinforcing fiber bundle Production of a resin-coated reinforcing fiber yarn, characterized in that molten thermoplastic resin is extruded from a discharge port into a hollow cylindrical shape, and the thermoplastic resin is brought into contact with the outer periphery of the reinforcing fiber bundle under a pressure-free condition to perform coating. Is the way.

The manufacturing method of the present invention will be described in detail below. 2 is a schematic side view showing an example of a coating apparatus used for carrying out the method of the present invention, FIG. 1 is a schematic sectional view of a crosshead die of the coating apparatus, and FIG. 3 is a schematic sectional view of a resin discharging portion of the crosshead die. Fig. 4 and Fig. 4 are A of Fig. 3.
FIG. Reference numeral 1 is a reinforcing fiber bundle formed by a large number of continuous reinforcing fibers, 2 is a yarn feeding device for supplying the reinforcing fiber bundle 1, 3 is a screw type extruder for melting and extruding resin, and 4 is reinforcing fiber A crosshead die for coating the outer periphery of the bundle 1 with resin, 5 is a resin-coated reinforcing fiber yarn, 6 is a thermoplastic resin cooling tank, and 7 is a winding device.

The crosshead die 4 has a fiber hole 10 for passing the reinforcing fiber bundle 1 in the center, and a cylindrical passage 11 around the hole for passing the molten resin, and an annular discharge port 12 at the lower end thereof. Has been formed. The fiber hole 10 is sized to allow the reinforcing fiber bundle 1 to pass through loosely. For example, when the reinforcing fiber bundle 1 has a circular cross section with a diameter of about 1 mm, the inner diameter of the fiber hole 10 is 2 to 4 m.
It is set to about m. The discharge port 12 is spaced from the fiber hole 10 through which the reinforcing fiber bundle 1 passes,
Therefore, the molten resin 14 discharged from the discharge port 12 can come into contact with the outer periphery of the reinforcing fiber bundle 1 in a pressure-free state. If the distance between the fiber hole 10 and the discharge port 12 is too large, it takes time for the resin 14 discharged from the discharge port 12 in a circular cross section to come into contact with the reinforcing fiber bundle 1.
Since it may not be possible to obtain the required adhesive strength, it is usually 2
It is selected to be not more than mm, preferably about 1 mm.

Next, a method of manufacturing the resin-coated reinforcing fiber yarn using the above apparatus will be described. First, the thermoplastic resin pellets are charged into the hopper 3a of the screw type extruder 3, heated and melted in the cylinder portion 3b, and introduced into the crosshead die 4 by a screw. The molten resin 14 introduced into the crosshead die 4 passes through the cylindrical passage 11 and is discharged in a cylindrical shape from the annular discharge port 12 at the lower end. On the other hand, the reinforcing fiber bundle 1 is pulled out from the yarn feeding device 2 and runs downward in the fiber hole 10 at the center of the crosshead die 4, and therefore,
The resin 14 discharged from the discharge port 12 surrounds the running reinforcing fiber bundle 1. The resin 14 discharged from the discharge port 12 contracts due to surface tension or cooling, and further contracts due to being pulled downward, so that the resin 14 comes into contact with the outer periphery of the reinforcing fiber bundle 1 and adheres to the continuous fibers in that portion. Thus, the resin 14 is coated and coated around the reinforcing fiber bundle 1. The resin-coated reinforcing fiber yarn 5 formed by this coating is then cooled by passing through the thermoplastic resin cooling tank 6 and wound up by the winding device 7.

In the above coating operation, the thermoplastic resin is discharged from the discharge port 12 and comes into contact with the outer periphery of the reinforcing fiber bundle 1 in a state where the pressure is released, that is, in a pressure free state. Therefore, the resin 14 contacting the reinforcing fiber bundle 1 is hardly impregnated between the continuous fibers inside. Thus, the resin-coated reinforcing fiber yarn having a structure in which the thermoplastic resin coating is bonded only to the continuous fibers located on the outer periphery of the reinforcing fiber bundle 1 is manufactured. Here, in order to ensure good adhesion between the continuous fibers located on the outer periphery of the reinforcing fiber bundle 1 and the thermoplastic resin coating that surrounds the continuous fibers, the molten resin 14 discharged from the discharge port 12 is not cooled and solidified so much. It is desirable to contact the reinforcing fiber bundle 1 with the
4 is a reinforcing fiber bundle 1 between 5 and 30 mm immediately below the discharge port 12.
It is better to contact with. Further, the discharge temperature condition of the thermoplastic resin is 30 to 60 ° from the melting point of the thermoplastic resin.
It is preferable that the temperature is about C higher. The viscosity of the molten resin at that time is preferably 10,000 poise or less.

The present invention also provides a molding material for producing a fiber-reinforced thermoplastic resin molded product using the above-mentioned resin-coated reinforcing fiber yarn of the present invention. Hereinafter, the molding material of the present invention will be described. One form of the molding material of the present invention is a woven fabric woven using the above-mentioned resin-coated reinforcing fiber yarn. This woven fabric may be one in which the above-mentioned resin-coated reinforcing fiber yarn is used for all of the warp and weft, or the above-mentioned resin-coated reinforcing fiber yarn is used for a part of the warp and weft, and the remainder is coated with the resin. It is also possible to use a thermoplastic resin fiber yarn of the same quality as the thermoplastic resin used for the reinforcing fiber yarn. In the latter case, the reinforcing fiber content of the molded product obtained by using this woven fabric can be adjusted by adjusting the ratio of the thermoplastic resin fiber yarn to be put into the woven fabric.

When a woven fabric is woven using the resin-coated reinforcing fiber yarn and the thermoplastic resin fiber yarn, the arrangement of both is arbitrary, and for example, the following combinations can be used. Resin-coated reinforcing fiber yarns and thermoplastic resin fiber yarns are used for both the warp yarns and the weft yarns. The resin-coated reinforcing fiber yarn or the thermoplastic resin fiber yarn is used for one of the warp yarn and the weft yarn, and only the resin-coated reinforcing fiber yarn is used for the other. The resin-coated reinforcing fiber yarn and the thermoplastic resin fiber yarn are used for one of the warp yarn and the weft yarn, and only the thermoplastic resin fiber yarn is used for the other. Only the resin-coated reinforcing fiber yarn is used for one of the warp yarn and the weft yarn, and only the thermoplastic resin fiber yarn is used for the other.

Suitable combinations of these may be selected according to the characteristics desired for the molded product. For example,
In this combination, the reinforcing fibers are arranged in both the warp and the weft, so that it is possible to obtain a reinforced molded body without directivity. On the other hand, in the combination of, since the reinforcing fibers are arranged in only one of the warp and the weft, it is possible to obtain a molded body reinforced in only one direction. Note that, even in the case of the above combination, when the woven fabrics are laminated so that the reinforcing fibers intersect each other, a molded product reinforced without directionality can be obtained.

As the weave structure of the woven fabric used in the present invention,
There is no particular limitation, and plain weave, twill weave and the like are optional.
Further, weaving can be performed by an ordinary loom as in the conventional case. In this weaving process, the warp and weft are bent or rubbed. However, since the resin-coated reinforcing fiber yarn of the present invention has appropriate flexibility, it is not damaged even when bent, and the thermoplastic resin coating covers the reinforcing fiber bundle that is easily rubbed and damaged. As a result, damage to the reinforcing fiber, fluffing, etc. do not occur. Further, since this thermoplastic resin coating is bonded to the continuous fibers on the outer periphery of the reinforcing fiber bundle, it does not peel off. Thus, the resulting fabric has no damage to the reinforcing fibers that make it up,
It also has flexible characteristics.

Next, a molding method using this woven fabric will be described. The woven fabrics are set in a mold by stacking a number of sheets corresponding to the wall thickness required for the molded body. Since this woven fabric is flexible, it has good shapeability and can be adapted not only to a flat shape but also to a curved surface. When setting the woven fabric in the mold, a resin film may be placed between the woven fabrics in order to adjust the reinforcing fiber content in the molded body, and in order to secure the necessary strength and rigidity, only the reinforcing fiber yarns are used. You may arrange | position the woven fabric which consists of these, or the prepreg etc. which the resin was impregnated by aligning the reinforcing fibers. However, since these resin films and prepregs deteriorate the shapeability, it is better to use a small number of them. Also, since a woven fabric made only of reinforcing fiber threads has a poor impregnating property, it is also preferable that a small number of these are used. . After setting in the mold, pressurization and heating are performed as in the conventional case. It is appropriate that the pressurization is about 5 to 20 kg / cm ² and the temperature is about 30 to 50 ° C. higher than the melting point of the resin used.
As a result, the thermoplastic resin is melted and impregnated between the reinforcing fibers to form a matrix. Then, by cooling and solidifying, a fiber-reinforced thermoplastic resin molded product is obtained.

In the resin-coated reinforcing fiber yarn, since the thermoplastic resin surrounds the reinforcing fiber bundle, the molten resin may have a short flowing distance during impregnation by heating under pressure. A reliable impregnation is obtained. Further, even at the intersections of the reinforcing fibers which are difficult to impregnate, the resin coating exists between the reinforcing fibers, so that impregnation failure does not occur at this portion. Thus, the obtained molded product has a good impregnation property, almost no voids, and excellent bending strength.

Another form of the molding material of the present invention is a braid braided using the above-mentioned resin-coated reinforcing fiber yarn.
The blade has a plurality of threads arranged in a spiral in the S direction (hereinafter referred to as S direction threads) and a plurality of threads arranged in a Z direction in a direction intersecting with the spiral (hereinafter referred to as Z direction threads). However, in the blade of the present invention, the above resin-coated reinforcing fiber yarn may be used for all of the S direction yarn and the Z direction yarn, or the S direction yarn,
Using the resin-coated reinforcing fiber yarn described above as a part of the Z-direction yarn,
A thermoplastic resin fiber yarn of the same quality as the thermoplastic resin used for the resin-coated reinforcing fiber yarn may be used for the balance. In the latter case, by adjusting the proportion of the thermoplastic resin fiber yarn to be put into the blade, the reinforcing fiber content of the molded product obtained by using this blade can be adjusted.

When the braid is braided using the resin-coated reinforcing fiber yarn and the thermoplastic resin fiber yarn, the arrangement of both is arbitrary, and for example, the following combinations can be used. A resin-coated reinforcing fiber thread and a thermoplastic resin fiber thread are used as both the S-direction thread and the Z-direction thread. The resin-coated reinforcing fiber yarn and the thermoplastic resin fiber yarn are used for one of the S-direction yarn and the Z-direction yarn, and only the resin-coated reinforcing fiber yarn is used for the other. The resin-coated reinforcing fiber yarn and the thermoplastic resin fiber yarn are used for one of the S-direction yarn and the Z-direction yarn, and only the thermoplastic resin fiber is used for the other. Only the resin-coated reinforcing fiber yarn is used for one of the S-direction yarn and the Z-direction yarn, and only the thermoplastic resin fiber yarn is used for the other.

Suitable combinations of these may be selected depending on the properties desired for the molded product. For example,
In this combination, since the reinforcing fibers are arranged in both the S-direction yarn and the Z-direction yarn, it is possible to obtain a reinforced molded body without directionality. On the other hand, in the combination of and, since the reinforcing fibers are arranged only in one of the S direction yarn and the Z direction yarn,
It is possible to obtain a molded product reinforced in only one direction. Note that, even in the case of the above combination, when the blades are laminated so that the reinforcing fibers are laminated so as to intersect with each other, it is possible to obtain a reinforced molded body having no directionality.

The braiding of the above-mentioned blade can be performed by a very general braiding machine without using a special device.
That is, the resin-coated reinforcing fiber yarn wound beforehand on the braiding pipe (and the thermoplastic resin fiber preliminarily wound on the braiding pipe as needed) is set in the right and left hand tube holders of the braiding machine. , This is made into a blade by a braiding machine. At this time, the resin-coated reinforcing fiber yarn is bent or rubbed, but as in the case of the above-mentioned weaving, the resin-coated reinforcing fiber yarn of the present invention has appropriate flexibility and therefore is bent. However, it is not damaged, and the reinforcing fiber is not damaged or fluffed. Furthermore, since this thermoplastic resin coating is adhered to the continuous fibers on the outer periphery of the reinforcing fiber bundle, it does not peel off. Thus, the obtained blade is one in which the reinforcing fibers constituting the blade are not damaged and have a flexible characteristic.

Since the blade of the present invention has a tubular shape, it is suitable for molding a fiber-reinforced thermoplastic resin tubular molding. Hereinafter, a method for forming a fiber-reinforced thermoplastic resin molded tube (FRTP tube) using this blade will be described. First, the core rod is covered with the number of blades corresponding to the required thickness of the molded body. At this time, since the blade is flexible, it is easy to handle and the covering work is easy.
When setting the blade on the core rod, in order to adjust the reinforcing fiber content in the molded body, a resin tube may be arranged between the blade layers, and in order to secure the necessary strength and rigidity, the blade layers are , 0, 90 °, etc., may be arranged in parallel, and a prepreg impregnated with resin by aligning reinforcing fibers, a woven fabric of reinforcing fibers, or the like may be arranged. However, since these resin films and prepregs deteriorate the shapeability, it is preferable that the number of them used is small, and since the woven fabric made of only the reinforcing fibers has poor impregnability, it is also preferable that the number used is small.

Next, the core rod is pulled out, and instead, an internal pressure tube made of silicon or the like is set. The set product is put in a predetermined mold, and nitrogen, air, gas, or the like is injected into the internal pressure tube while heating and pressurized. Pressurization is 5
It is suitable that the temperature is about 20 kg / cm ² and the temperature is about 30 to 50 ° C. higher than the melting point of the resin used. By this heating and pressing, the thermoplastic resin is melted and impregnated between the reinforcing fibers to form a matrix. After that, the mold is cooled, the molten thermoplastic resin matrix is solidified, and the molded product is taken out from the mold. Through the above steps, a hollow molded body of a thermoplastic resin reinforced with continuous fibers can be obtained. The obtained molded body has almost no voids and exhibits very excellent bending strength and torsional strength due to the effect of the reinforcing fiber.

[0029]

The resin-coated reinforcing fiber yarn of the present invention has a structure in which a reinforcing fiber bundle composed of a large number of continuous fibers is covered with a thermoplastic resin coating, and the thermoplastic resin is almost impregnated inside the reinforcing fiber bundle. Therefore, it has flexibility even though the resin content is as high as 40 to 60%, and the thermoplastic resin coating on the outer periphery protects the reinforcing fiber bundles inside, so that weaving, braiding, etc. It is possible to prevent damage to the reinforcing fiber in the process. In addition, since the thermoplastic resin coating is adhered to the continuous fibers on the outer periphery of the reinforcing fiber bundle and has an appropriate thickness, weaving,
It does not come off during the process such as string making. Therefore, it can be suitably used as a material for a woven fabric or a blade used as a molding material for producing a fiber-reinforced thermoplastic resin molding.

According to the method of the present invention, a thermoplastic resin is extruded into a hollow cylindrical shape so as to surround the reinforcing fiber bundle while running the reinforcing fiber bundle formed of a large number of continuous reinforcing fibers, and the pressure is applied. Since it is configured to contact the outer periphery of the reinforcing fiber bundle in a free state, the resin-coated reinforcing fiber yarn of the present invention can be manufactured by adhering the resin to the continuous fibers on the outer periphery without impregnating the inside of the reinforcing fiber bundle with resin. . At this time, since the thermoplastic resin may be extruded in a molten state and then brought into contact with the outer circumference of the reinforcing fiber bundle in a pressure-free state, it is possible to increase the processing speed (traveling speed of the reinforcing fiber bundle). Yes, for example, it can be set to about 200 m / min. Therefore, the production efficiency can be increased.

The molding material made of a woven fabric woven with the above-mentioned resin-coated reinforcing fiber yarn is flexible because it uses the flexible resin-coated reinforcing fiber yarn, and therefore has good shapeability and has a curved surface. It is suitable for forming molded articles and has excellent workability during lamination and shaping. Further, since the outer periphery of the reinforcing fiber bundle is uniformly coated with the thermoplastic resin, the impregnating property at the time of molding is good, the impregnating property is good even at the intersections of the reinforcing fibers in the fabric, and the dispersibility of the reinforcing fibers is good. Good. Therefore, it is possible to perform molding under low pressure for a shorter time.

As in the case of the woven fabric, the molding material composed of the braid formed by using the above-mentioned resin-coated reinforcing fiber yarn is also flexible because it uses the flexible resin-coated reinforcing fiber yarn, as in the case of the woven fabric. Good formability and excellent workability during lamination and shaping. Further, since the outer periphery of the reinforcing fiber bundle is uniformly coated with the thermoplastic resin, the impregnating property at the time of molding is good, the impregnating property is good even at the intersections of the reinforcing fibers in the fabric, and the dispersibility of the reinforcing fibers is good. Good. Therefore, it is possible to perform molding under low pressure for a shorter time. Since this blade has a tubular shape, it is suitable for molding a fiber-reinforced thermoplastic resin tubular molded body.

[0033]

【Example】

Example 1 A resin-coated reinforcing fiber yarn was produced under the following conditions, and the following results were obtained. (1) Materials used Reinforcing fiber bundle: Carbon fiber HTA-6KCF (manufactured by Toho Rayon Co., Ltd.) Number of filaments 6000 Filament diameter 7 μm Thermoplastic resin: Polyamide PA6 (manufactured by Ube Industries, Ltd.)

(2) Coating conditions Equipment used: configuration shown in FIGS. 1 to 4 Inner diameter of fiber hole 10: 3.5 mm Outer diameter of outlet 12: 7 mm, inner diameter: 5.5 mm Crosshead die temperature: 270 ° C. Cylinder temperature of extruder 3: 250 ° C Discharge amount of thermoplastic resin: 46 g / min Winding speed: 200 m / min

(3) Results A resin-coated reinforcing fiber yarn having a thermoplastic resin coating on the outer periphery of the reinforcing fiber bundle was obtained. The reinforcing fiber volume content of the obtained resin-coated reinforcing fiber yarn was 54%. When the resin-coated reinforcing fiber yarn was cut and the cross section was observed with an electron microscope, a thermoplastic resin coating surrounding the reinforcing fiber bundle was formed, and the coating was adhered to the continuous fibers on the outer periphery of the reinforcing fiber bundle. It was Further, resin impregnation inside the reinforcing fiber bundle was not observed. Furthermore, when the thermoplastic resin coating was peeled off and the reinforcing fiber bundle inside was observed, no damage was found on the reinforcing fiber inside, and therefore no damage was generated on the reinforcing fiber during the coating process. The obtained resin-coated reinforcing fiber yarn was soft, and when a weaving test was conducted, it was possible to weave without causing damage.

Example 2 A resin-coated reinforcing fiber yarn was produced under the following conditions, and the following results were obtained. (1) Materials used Reinforcing fiber bundle: Carbon fiber HTA-6KCF (manufactured by Toho Rayon Co., Ltd.) Number of filaments 6000 Filament diameter 7 μm Thermoplastic resin: Polyphenylene sulfide PPS (manufactured by Dainippon Ink and Chemicals, Inc.)

(2) Coating conditions Apparatus used: configuration shown in FIGS. 1 to 4 Inner diameter of fiber hole 10: 3.5 mm Outer diameter of outlet 12: 7 mm, inner diameter: 5.5 mm Crosshead die temperature: 320 ° C. Cylinder temperature of extruder 3: 290 ° C Thermoplastic resin discharge rate: 46 g / min Winding speed: 200 m / min

(3) Results A resin-coated reinforcing fiber yarn having a thermoplastic resin coating on the outer periphery of the reinforcing fiber bundle was obtained. The reinforcing fiber volume content of the obtained resin-coated reinforcing fiber yarn was 54%. This resin-coated reinforcing fiber yarn also had the same characteristics as those of Example 1.

Example 3 A resin-coated reinforcing fiber yarn was produced under the following conditions, and the following results were obtained. (1) Materials used Reinforcing fiber bundle: Carbon fiber HTA-6KCF (manufactured by Toho Rayon Co., Ltd.) Number of filaments 6000 Filament diameter 7 μm Thermoplastic resin: Polyamide PA6 (manufactured by Ube Industries, Ltd.)

(2) Coating conditions Equipment used: configuration shown in FIGS. 1 to 4 Inner diameter of fiber hole 10: 3.5 mm Outer diameter of outlet 12: 7 mm, inner diameter: 5.5 mm Crosshead die temperature: 280 ° C. Cylinder temperature of extruder 3: 250 ° C Discharge amount of thermoplastic resin: 30 g / min Winding speed: 130 m / min

(3) Results A resin-coated reinforcing fiber yarn having a thermoplastic resin coating on the outer periphery of the reinforcing fiber bundle was obtained. The reinforcing fiber volume content of the obtained resin-coated reinforcing fiber yarn was 54%. This resin-coated reinforcing fiber yarn also had the same characteristics as those of Example 1.

Example 4 A resin-coated reinforcing fiber yarn was produced under the following conditions, and the following results were obtained. (1) Materials used Reinforcing fiber bundle: Carbon fiber HTA-12KCF (manufactured by Toho Rayon Co., Ltd.) Number of filaments 12000 Filament diameter 7 μm Thermoplastic resin: Polyamide PA6 (manufactured by Ube Industries, Ltd.)

(2) Coating conditions Apparatus used: configuration shown in FIGS. 1 to 4 Inner diameter of fiber hole 10: 5 mm Outer diameter of outlet 12: 9 mm, inner diameter: 7 mm Crosshead die temperature: 270 ° C. Extruder 3 Cylinder temperature: 250 ° C Thermoplastic resin discharge rate: 30 g / min Winding speed: 65 m / min

(3) Results A resin-coated reinforcing fiber yarn having a thermoplastic resin coating on the outer periphery of the reinforcing fiber bundle was obtained. The reinforcing fiber volume content of the obtained resin-coated reinforcing fiber yarn was 54%. This resin-coated reinforcing fiber yarn also had the same characteristics as those of Example 1.

Example 5 Using the resin-coated reinforcing fiber yarn of Example 3, a woven fabric was woven under the following conditions. Woven structure: plain weave Weave density: 10 warps / 25 mm, 10 wefts / 25 mm The obtained woven fabric was soft, and neither warp nor weft was damaged. Using this woven fabric, a flat plate was formed under the following conditions. Lamination structure: 8 ply Molding condition: 270 ° C., 10 kgf / cm ² , 10 mi
n By this molding, a molded body having a thickness of 2.1 mm was obtained. The results of measuring the mechanical properties of this molded product are shown in Table 1.

Comparative Example 1 A woven fabric and a thermoplastic resin film having the following specifications of reinforcing fiber bundles only were prepared. Reinforcing fiber fabric Fibers used: carbon fiber T-300 6KCF fabric (manufactured by Toray Industries, Inc.) Number of filaments 6000 filament diameter 7 μm Woven structure: plain weave Weave density: 10 warps / 25 mm, 10 wefts / 25 mm Thermoplastic resin: polyamide PA6 Film thickness 60 μm (manufactured by Unitika Ltd.) Using this reinforcing fiber woven fabric and thermoplastic resin film,
A flat plate was formed under the following conditions. Lamination structure: PA6 so that the surface is a PA6 film
Films and reinforcing fiber fabrics were alternately laminated, and eight reinforcing fiber fabrics were laminated. Molding conditions: 270 ° C, 10 kgf / cm ² , 10 mi
n By this molding, a molded body having a thickness of 2.2 mm was obtained. The results of measuring the mechanical properties of this molded product are shown in Table 1.

[0047]

[Table 1]

As can be seen from Table 1, the molded product obtained in Example 5 had extremely excellent characteristics as compared with the molded product obtained in Comparative Example 1 obtained from the conventional reinforcing fiber woven fabric.

Example 6 Using the resin-coated reinforcing fiber yarn of Example 4, a braid was braided under the following conditions. Number of shots: 24 Shot angle: 30 ° Blade diameter: 18 mm The obtained blade was flexible, and no damage was observed on the resin-coated reinforcing fiber yarn. Using this blade, a FRTP tube was molded under the following conditions. Lamination structure: 3 ply Molding condition: 260 ° C., internal pressure 10 kgf / cm ² , 20
Mold release at min, cooling 15 ° C / min, 80 ° C or less The FRTP tube obtained had an outer diameter of 20 mm and a wall thickness of 1.2 mm, and the reinforcing fiber volume content was 55%. The results of measuring the mechanical properties are shown in Table 2.

Comparative Example 2 A 12KCF / PA6 mixed woven type blade was produced under the following conditions, and an FRTP pipe was formed by internal pressure forming using the blade. (1) Materials used Reinforcing fiber bundle: Carbon fiber HTA-12KCF (manufactured by Toho Rayon Co., Ltd.) Number of filaments 12000 Filament diameter 7 μm Thermoplastic resin fiber: Polyamide PA6 (manufactured by Ube Industries, Ltd.) 72 filaments Filament diameter 82 μm Yarn Count 460TEX

(2) Braiding Conditions Number of Strokes: 48 Strokes Angle: 30 ° Blade Diameter: 18 mm Both left and right turns are made of carbon fiber and nylon fiber braid pipes, and the reinforcing fibers cross each other. A mixed woven type blade was produced in which equal amounts were arranged in the same direction.

(3) Internal pressure molding Using the blade obtained, an FRTP tube was molded under the following conditions. Laminated structure: 3 ply Molding condition: 260 ° C, internal pressure 8 kgf / cm ² , 10 m
in, cooling at 15 ° C / min, demolding at 80 ° C or less The obtained FRTP tube had an outer diameter of 20 mm and a wall thickness of 1.2 mm, and the reinforcing fiber volume content was 55%. The results of measuring the mechanical properties are shown in Table 2.

Comparative Example 3 A 12KCF / PA6 one-way type blade was prepared under the following conditions, and an FRTP pipe was formed by internal pressure molding using the blade. (1) Materials used Reinforcing fiber bundle: Carbon fiber HTA-12KCF (manufactured by Toho Rayon Co., Ltd.) Number of filaments 12,000 filament diameter 7 μm Thermoplastic resin fiber: Nylon fiber PA6 (manufactured by Ube Industries, Ltd.) 72 filaments Filament diameter 82 μm Thread count 460TEX

(2) Braiding Conditions Number of Strokes: 32 Strokes Angle: 30 ° Blade Diameter: 18 mm So-called Z direction, in which a tube made of carbon fiber is attached to the left-handed tube and nylon fiber is attached to the right-handed tube. A so-called S-direction reinforcing blade was produced by braiding a reinforcing blade, a right-handed tube insert with carbon fiber, and a left-handed tube insert with a nylon fiber cord.

(3) Internal pressure molding Using the blade obtained, an FRTP tube was molded under the following conditions. Lamination structure: 4ply Molding conditions: 260 ° C, internal pressure 8kgf / cm ² , 10m
in, cooling at 15 ° C / min, demolding at 80 ° C or less The obtained FRTP tube had an outer diameter of 20 mm and a wall thickness of 1.1 mm, and the reinforcing fiber volume content was 55%. The results of measuring the mechanical properties are shown in Table 2.

[0056]

[Table 2]

As can be clearly seen from Table 2, the molded body obtained in Example 6 had extremely excellent properties as compared with those of Comparative Examples 2 and 3 obtained from the conventional reinforcing fiber blade.

[0058]

As described above, in the resin-coated reinforcing fiber yarn of the present invention, the reinforcing fiber bundle composed of a large number of continuous fibers is covered with the thermoplastic resin coating for protection, and has appropriate flexibility. Since it does not cause damage in the process of weaving, stringing, etc., it can be suitably used as a material for a woven fabric or a blade used as a molding material for manufacturing a fiber-reinforced thermoplastic resin molded body. In addition, at the time of molding, the resin has a good impregnation property with respect to the reinforcing fiber, and it has an effect that a high quality molded body can be molded. Further, since the resin-coated reinforcing fiber yarn is integrated with the reinforcing fiber in the form of being coated with a thermoplastic resin, as compared with a prepreg yarn formed by fiberizing and then twisting or commingling with the reinforcing fiber, The manufacturing process is simple and can be manufactured at low cost. Furthermore, since the reinforcing fibers are protected by the thermoplastic resin coating, they do not come apart in the subsequent process, and therefore the number of single fibers constituting the reinforcing fiber bundle can be reduced. It is possible to increase the number, and it also has the effect of good productivity.

The molding material of the present invention comprising a woven fabric obtained by weaving the above-mentioned resin-coated reinforcing fiber yarn is flexible because it uses the flexible resin-coated reinforcing fiber yarn, and therefore has good shapeability. Suitable for forming a molded article having a curved surface, excellent in workability during lamination and shaping, and because the outer periphery of the reinforcing fiber bundle is uniformly coated with a thermoplastic resin, good impregnation during molding, The impregnating property is good even at the intersections of the reinforcing fibers in the fabric, and the dispersibility of the reinforcing fibers is good. Therefore, there is an effect that molding can be performed for a shorter time at a low pressure, a molded body with few voids and a high reinforcing effect can be produced.

Like the case of the woven fabric, the molding material of the present invention, which is composed of a braid formed by using the above-mentioned resin-coated reinforcing fiber yarn, is flexible because it uses the flexible resin-coated reinforcing fiber yarn. Therefore, the shapeability is good, the workability at the time of lamination and shaping is excellent, and since the outer periphery of the reinforcing fiber bundle is uniformly coated with the thermoplastic resin, the impregnation property at the time of molding is good, and the fabric The impregnating property is good even at the intersections of the reinforcing fibers inside, and the dispersibility of the reinforcing fibers is good. Therefore, it is possible to perform molding under a low pressure for a shorter time, it is possible to make a molded body with few voids and a high reinforcing effect, and it is extremely suitable for molding a fiber-reinforced thermoplastic resin tubular molded body. Have an effect.

In the method of the present invention, a thermoplastic resin is extruded into a hollow cylindrical shape so as to surround the reinforcing fiber bundle while running the reinforcing fiber bundle formed of a large number of continuous reinforcing fibers, and the pressure is applied. Since it is configured to contact the outer periphery of the reinforcing fiber bundle under free conditions, the resin-coated reinforcing fiber yarn of the present invention can be manufactured by adhering the resin to the continuous fiber on the outer periphery without impregnating the inside of the reinforcing fiber bundle. At this time, the molten thermoplastic resin may be brought into contact with the outer circumference of the reinforcing fiber bundle under pressure-free conditions, so that the processing speed (traveling speed of the reinforcing fiber bundle) can be increased and the production efficiency can be improved. It has the effect that it can be raised.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a crosshead die of an example of a coating apparatus used for carrying out a manufacturing method of the present invention.

FIG. 2 is a schematic side view of the coating apparatus.

FIG. 3 is a schematic cross-sectional view of a resin discharge portion of the crosshead die.

FIG. 4 is a view on arrow AA of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reinforcement fiber bundle 2 Yarn supply device 3 Screw type extruder 4 Crosshead die 5 Resin-coated reinforcement fiber yarn 6 Thermoplastic resin cooling tank 7 Winding device 10 Fiber hole 11 Cylindrical passage 12 Discharge port 14 Resin

Claims (6)

[Claims] 1. A resin-coated reinforcing fiber yarn used for producing a fiber-reinforced thermoplastic resin molding, comprising a reinforcing fiber bundle formed of a large number of reinforcing continuous fibers, and an outer periphery of the reinforcing fiber bundle. Consisting of a thermoplastic resin coated on the thermoplastic resin, the thermoplastic resin is almost not impregnated inside the reinforcing fiber bundle, and is adhered to continuous fibers located on the outer periphery,
Further, the resin coated reinforcing fiber yarn is characterized in that the reinforcing continuous fiber has a volume content of 40 to 60%. 2. A molding material for producing a fiber-reinforced thermoplastic resin molding, the molding material comprising a woven fabric woven using the resin-coated reinforcing fiber yarn according to claim 1. 3. A molding material for producing a fiber-reinforced thermoplastic resin molding, comprising the resin-coated reinforcing fiber yarn according to claim 1 and a thermoplastic resin used for the resin-coated reinforcing fiber yarn. A molding material comprising a woven fabric woven using the same quality thermoplastic resin fiber yarn. 4. A molding material for producing a fiber-reinforced thermoplastic resin molding, comprising a braid braided with the resin-coated reinforcing fiber yarn according to claim 1. 5. A molding material for producing a fiber-reinforced thermoplastic resin molding, comprising: the resin-coated reinforcing fiber yarn according to claim 1; and a thermoplastic resin used for the resin-coated reinforcing fiber yarn. A molding material comprising a braid braided using a thermoplastic resin fiber yarn of the same quality. 6. An annular spout disposed so as to surround the reinforcing fiber bundle and not to contact the reinforcing fiber bundle while the reinforcing fiber bundle formed of a large number of continuous reinforcing fibers is running. Production of resin-coated reinforced fiber yarn, characterized in that molten thermoplastic resin is extruded from the outlet into a hollow cylindrical shape, and the thermoplastic resin is brought into contact with the outer periphery of the reinforcing fiber bundle under pressure-free condition to perform coating. Method.