JPH0693579A - Composite material and its production - Google Patents

Abstract

PURPOSE:To efficiently obtain through a simplified process a filamentous composite material by reinforcing a thermosetting resin with high-strength fibers. CONSTITUTION:Tension is applied on a plurality of high-strength fiber bundles, which are then individually impregnated 2 with a resin; the volatiles in the resin are expelled by heating and drying 3 each of the bundles, which are then gathered 4 into a composite elemental strand 8. In this case, the bundle gathering position is fixed relatively to the cross-sectional plane for the elemental strand and the bundles are arranged in parallel with the axis of the elemental strand followed by covering the elemental strand through knitting/braiding, thus obtaining the objective filamentous composite material. For the composite material, either directly or after twisted, the resin impregnated above is cured, thus obtaining the other objective single or twisted filamentous composite material 14.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an uncured wire of a filament composite material in which a thermosetting resin is reinforced with high-strength fibers, a single wire obtained by thermosetting a single uncured wire, and a plurality of uncured wires. The present invention relates to a filament product obtained by twisting a strand or thermosetting without stranding, and a method for producing the same.

Such a composite material can be used alone as a brace material for bridge main cables or constructions, and by combining it with concrete or mortar, it can be used as a tension material for prestressed concrete, a rock bolt material for ground reinforcement, and a reinforced concrete material. It can be used as a reinforcing bar substitute.

Since this composite material is lighter in weight than conventional steel materials and is excellent in corrosion resistance, salt damage resistance and machinability, it can be directly excavated by a ground reinforcement rock bolt or a shield machine in a deep underground space. It can also be applied to members that have been difficult with conventional materials such as reinforcing materials for vertical shaft concrete members.

[0004]

2. Description of the Related Art As a manufacturing technique for a rod-shaped thermosetting resin composite material, there is a manufacturing technique by a pultrusion method or a manufacturing technique for bundling composite material strands like a cable.

The manufacturing technique by the pultrusion method is a continuous pultrusion molding method for a rod-shaped composite material, in which a high-strength fiber yarn impregnated with a thermosetting resin is passed through a heating die to be continuously drawn and cured to obtain a product. It is a technology.

Although the pultrusion method can manufacture raw materials to final products at once, it has a drawback that it is difficult to manufacture long products.

In addition, a large diameter pultrusion product has a large bending rigidity, which makes handling somewhat difficult.

Further, there is also a problem that the pull-thru product is cracked in the axial direction due to the stress due to the internal shrinkage of the resin at the time of thermosetting, and it is very difficult to manufacture the large-diameter pultrusion product.

On the other hand, a cable or wire can be used with an arbitrary diameter by bundling a large number of element wires of an arbitrary length according to the use environment and load.

Since the bending rigidity of the bundle is smaller than that of the pultrusion product having the same cross-sectional area, the bundle can be wound on a drum or the like, so that the handling is easy.

Even when the fiber-reinforced composite material is used as a cable, it is convenient from the viewpoint of handling that it is used as a stranded wire as seen in the conventional steel wire wire in order to prevent the individual cables from loosening. .

In order to produce a stranded wire made of these composite materials, a wire in which the resin is not cured is produced by some method, and the uncured wire is twisted to form an uncured stranded wire and then heated. It is necessary to harden the wire into a completely hardened stranded wire.

When the fiber-reinforced composite material using the thermosetting resin is completely cured, it is close to an elastic body and hardly causes plastic deformation.

Therefore, even if a completely hardened wire is used to form a stranded wire, it is difficult to process due to a very large untwisting force, and even if it is processed, the shape is worse and the quality and appearance are good. Because there is no.

If an uncured element wire is used, the uncured resin undergoes plastic deformation, so that it can be easily processed into a stranded wire.

The processing of the final product through the uncured element wire is a characteristic of the manufacturing method when the composite material is used as a cable, and is different from the manufacturing method by the pultrusion capable of manufacturing the final product at once. Is.

As a method of manufacturing such a composite material, there are a conventional manufacturing method as disclosed in JP-B-62-18679 and a manufacturing method as disclosed in JP-A-2-127583.

That is, the manufacturing method as disclosed in Japanese Examined Patent Publication No. Sho 62-18679 is to form a fiber core by means such as bundling, twisting or braiding of fibers having high strength and low elongation, and heat the fiber core with heat. It is a manufacturing method in which a curable resin is impregnated, the peripheral surface of the fiber core is sprinkled with a dry powder agent, and the outer periphery of the fiber core is covered with a braided body of fibers.

The manufacturing method as disclosed in Japanese Patent Application Laid-Open No. 2-127583 refers to a strand prepreg (hereinafter referred to as a strand prepreg obtained by impregnating a multi-filament of high strength and low elongation fiber with a thermosetting resin and semi-curing the resin. An uncured yarn) is formed, and a plurality of uncured yarns are twisted together to form a composite strand yarn, and the outer periphery of the composite strand yarn is densely wound in a state close to a right angle to the axial direction to cover the outer periphery. Is the way.

At this time, it is also described that a porous tape may be used instead of using the fiber coating, and that the pitch at which the wires are twisted together should be 8 times or more the finished diameter of the twisted wire. is there.

Further, in Japanese Patent Application Laid-Open No. 2-104786, high strength and low elongation fibers are collected by means such as bundling, twisting and braiding to form a fiber core, and the fiber core is impregnated with a thermosetting resin. Then, the outer periphery of the fiber core is covered with a dense coating by winding or braiding a coating material, and then the fiber core is heated to cure the thermosetting resin therein to obtain a composite filament. When a coating is applied to the outer periphery of the fiber core, a material corresponding to the coating is given an elongation corresponding to the heat shrinkage rate of the thermosetting resin impregnated in the fiber core, in advance. Is listed.

[0022]

However, even with the above method, there are some problems. That is, the manufacturing speed is slow, the manufacturing process is complicated, and the cost is high.

That is, the method of Japanese Patent Publication No. 62-18679 is a method in which a plurality of reinforcing fibers are bundled, twisted, braided or the like to form a fiber core, and then a thermosetting resin is impregnated.

Therefore, it becomes difficult to completely impregnate the thick fiber core with the resin as compared with the high-strength fiber yarn before bundling, and the incomplete impregnation state lowers the strength development rate.

Further, even if the impregnation is almost completely performed, the time required for impregnation becomes long and the production speed becomes slow.

Also, when the volatile components of the resin are dried, the fact that the fiber core is thick and the specific surface area is small is the rate-determining mechanism of the drying mechanism, which slows down the production rate.

In order to handle them, a filler which is originally useless must be used for manifesting the strength of the fiber reinforced composite material such as a dry powder, and a great labor is required for densely braiding the fibers.

Thus, impregnating or drying the thermosetting resin after forming the fiber core with the reinforcing fibers remarkably lowers the production rate, and requires a great deal of labor such as treatment with new dry powder and dense braiding treatment. I need.

Further, in the method disclosed in Japanese Patent Laid-Open No. 2-127583, a manufacturing step is a manufacturing step in which an uncured yarn is manufactured and a plurality of them are twisted to form a composite strand, that is, a twisted element wire.

According to another known document (Japanese Examined Patent Publication No. 57-25679), the effect of twisting is that even when the roundness of the uncured wire is maintained and it becomes a rope through various manufacturing processes. It is disclosed that the shape is substantially circular.

Further, the same document also discloses that the strength is lowered by twisting fibers having a low elongation.

In another publicly known document (Abstracts of the 13th Symposium of the Japan Society for Composite Materials, B-7), the twist inside the uncured wire is prevented depending on the twist angle, and the kink is prevented. It is disclosed.

In order to twist an uncured yarn into an uncured wire, it is necessary to divide into two steps, a manufacturing step of the uncured yarn and a step of twisting the uncured yarn, which makes the manufacturing facility large and complicated. .

Although a method of continuing the manufacturing process is also conceivable, when adding a real twist to the aggregate of uncured yarn, the upper process of the manufacturing line is rotated like a ferris wheel, or the lower process or a large turntable is used. It is practically impossible because it is necessary to rotate at a high peripheral speed by using.

Further, when the uncured yarn is manufactured, since the handling for rewinding the yarn into the bobbin is inserted, there is a possibility that the strength of the yarn such as a kink of the yarn is lowered during the handling.

Twisting the uncured yarn into an uncured wire in this way has advantages such as shape retention and kink prevention, but the complexity of the manufacturing process and the possibility of introducing a new cause of strength reduction There is also a drawback.

If shape retention and kink prevention are realized by other methods, the twisting process can be omitted and the production of uncured yarn to production of uncured filament can be performed in a continuous process, simplifying the production process. It is possible to prevent the introduction of a new cause of strength reduction.

To restate the problems of the prior art described above in detail, firstly, a yarn form in which the resin is rapidly impregnated into the reinforcing fiber yarn and dried quickly is established, and the strength development rate is high. And to speed up the production speed, the second is to prevent the shape of the uncured wire and the kink inside the uncured wire by a method other than the twisting process to make the manufacturing process continuous and simplify it. Is.

Next, in the method of Japanese Patent Laid-Open No. 2-104786, when the heat shrinkage of the coating is smaller than that of the thermosetting resin,
The coating does not follow the contraction of the fiber core, as a result, voids occur between the fiber core and the coating or inside the fiber core, the compactness with the composite filament decreases, and the cross-sectional shape becomes non-uniform, This is a technology that avoids adverse effects on strength.

However, in this method, the adhesion between the fiber core and the coating can be improved, but since the tightening pressure of the fiber core is small, the inside of the fiber core is not sufficiently improved.

[0041]

The present invention has been made to solve the above problems.

That is, the first is to establish a yarn form in which the inside of the reinforcing fiber yarn is rapidly impregnated with the resin and to be dried quickly so that the strength development rate is high and the production speed is high, and the second is a method other than the twisting treatment. The shape of the uncured wire and kinks inside the uncured wire are prevented and the manufacturing process is made continuous to simplify the above. -The purpose of the present invention is to provide a twisted wire and a manufacturing method thereof, and the summary thereof is as follows.

That is, a plurality of high-strength fiber yarns such as carbon fiber, glass fiber, and aramid fiber are run under a constant tension, each yarn unit is impregnated with a thermosetting resin, and each yarn unit is dried in a heating furnace. When the uncured yarns are processed and the multiple uncured yarns are bundled into a composite material strand, each uncured yarn is placed at a fixed position in the cross section of the composite material strand. While uncured yarns are bundled so as to be aligned parallel to the axial direction of the composite material strands, and the outer periphery of the bundled uncured yarns is covered with a fiber such as a braid, etc., or a carbon fiber , A process of running a plurality of high-strength fiber yarns such as glass fiber and aramid fiber under a constant tension and impregnating a thermosetting resin for each yarn unit, a process of heating and drying them into an uncured yarn, a plurality of them of When consolidating the hardened yarns into a composite material strand, each uncured yarn is placed at a fixed focusing position within the cross section of the composite material strand, and the uncured yarn is placed on the axis of the composite material strand. It is characterized in that the whole manufacturing process of the composite material wire consisting of a step of bundling so as to be aligned parallel to the direction and a step of covering the outer periphery of the bunched uncured yarn with a fiber etc. A composite material wire manufactured by the method for manufacturing a composite material wire, a composite material single wire manufactured by curing a thermosetting resin impregnated in a single composite material wire, and a plurality of composite material wires twisted together And a method for producing the same, which is a composite material twisted wire produced by curing an impregnated thermosetting resin by a method such as heating.

Further, each strand of fiber is individually impregnated with a thermosetting resin, and each strand is individually dried in a heating furnace to form an uncured strand, and the uncured strand is twisted. In the method for manufacturing a composite material filament element wire, which is bundled so as to be aligned in parallel without braiding, and the outer periphery of the bundled uncured strand is covered with a fiber such as a braid.
This is a method in which coating is performed using a high shrinkage yarn, and the tightening pressure of the uncured strand is increased during curing to improve the tensile strength of the cured strand with a dense structure.

Even when impregnated after assembling and then coated, the effect of improving strength is remarkably improved by coating with the highly shrinkable yarn of the present invention.

[0046]

The operation of the present invention will be described in detail below with reference to the drawings.

1 and 2 schematically show an example of a method for manufacturing a composite material strand according to the present invention. FIG. 1 is a plan view of the composite material strand manufacturing process, and FIG. 2 is a side view thereof.

The bobbin of the high-strength fiber yarn 7 is attached to the bobbin holder installed on the creel 1, and the high-strength fiber yarn 7 is unwound. The high-strength fiber includes carbon fiber, glass fiber, aramid fiber, silicon carbide fiber and the like.

These high strength fibers are usually supplied in the form of a plurality of filaments, generally 1000 to 20 filaments.
It is obtained in the form of a bundle of 000 filaments.

In the present invention, the high-strength fiber of these plural filaments is called a high-strength fiber yarn 7.

The high-strength fiber yarns 7 are individually unwound from the creel 1 in yarn units, and do not form fiber cores. A tension brake is installed on each bobbin holder, and uniform tension is applied to the high-strength fiber yarn.

The tension of the high-strength fiber yarn depends on the number of filaments constituting the yarn, but the tension of the PAN-based CF is 120.
About 1.0 kgf for 00 yarns, 30 for pitch-based CF
About 0.5 kgf of 00 yarns gives a relatively high tension for handling a high-strength fiber yarn.

The unwound high-strength fiber yarn 7 is impregnated with the thermosetting resin in the resin impregnation tank 2.

In the present invention, a state in which the high-strength fiber yarn 7 is impregnated with the thermosetting resin is called an uncured yarn 9.

At the time of impregnation, the high-strength fiber yarns 7 are individually impregnated in yarn units. This results in almost complete impregnation in a short time.

As the thermosetting resin, in addition to general epoxy resin and unsaturated polyester resin, flame-retardant epoxy resin, high toughness epoxy resin and phenol resin, polyimide having heat-resistant skeleton, polyamide imide and the like are used. Resin is used.

Further, with respect to thermosetting resins which are solid at room temperature, it is possible to dilute them with a solvent which dissolves those resins so that they can be impregnated.

The curing agent is selected according to use conditions and curing conditions. A liquid curing agent is suitable, but a solid curing agent may be dissolved in a solvent and used.

The uncured yarn 9 is heated and dried in the next heating and drying furnace 3. By this heat drying, when impregnated with a solvent, the solvent is removed from the uncured yarn 9,
The volatile matter contained in the resin is removed.

Also in this case, the uncured yarn 9 can be dried individually in units of yarn, so that the production speed can be increased.

When a solvent is used, the residual solvent ratio of the uncured yarn 9 after heating and drying is 1.2% or less. This is because the uncured yarn having a high residual ratio of the solvent causes a remarkable decrease in viscosity of the thermosetting resin at the time of final curing, which deteriorates the appearance of the product.

Even when the uncured yarn 9 is dried with a solvent, a sufficient amount of heat required for solvent drying can be provided in a normal heating and drying oven. Therefore, in order to further increase the production speed, a plurality of composite material strand processes can be used. The uncured yarns 9 required for the above can be arranged in multiple stages in the heating and drying oven 3 to perform solvent drying in one heating and drying oven.

After that, the uncured yarn 9 is aligned in parallel with the axial direction of the composite material strand while the focusing position of the uncured yarn 9 is set at a fixed position in the cross section of the composite material strand. To be focused.

It is desirable that the uncured yarns 9 are uniformly arranged in a plane so that the uncured yarns 9 have a shape substantially similar to the arrangement of the composite material strands in the cross section. Fig. 3 shows uncured yarn 9
Are schematically arranged in a plane and are then focused.

The uncured yarns 9 arranged almost uniformly are narrowed down in the yarn interval without breaking the arrangement, and finally bundled to a size close to the outer diameter of the product. After focusing, the uncured yarn 9 remains aligned in parallel.

By using this focusing device, the uncured yarn 9 can maintain a stable positional relationship during focusing, so that the shape of the composite material wire 8 and the kink inside the wire can be almost completely prevented.

FIG. 4 and FIG. 5 show schematic views of unstable uncured yarn arrangement. In both the examples in both figures, the uncured yarn collapses in the initial arrangement and is focused, so the position relationship of the uncured yarn during focusing changes in a time series, causing cross-sectional changes and partial kink. The shape of the composite material wire and the kink inside the wire cannot be prevented.

From the creel 1 to the bundling device 4, each reinforcing fiber yarn maintains a constant tension by an individual brake, and even if an unstable movement of the uncured yarn 9 occurs at the time of bundling, it is caused by the back tension. Be pulled back.

In the examples of the publicly known document (Japanese Patent Laid-Open No. 63-75194), it is disclosed that the uncured yarn is not limited to braiding or twisting, but it is disclosed that a core is formed by combining yarns and coating the core. However, as described above, it is not possible to prevent disorder of the arrangement of the uncured yarns, that is, a kink inside the strand, even if the yarns are simply combined.

In order to prevent kinks inside the strands, the uncured yarns 9 are uniformly arranged in a plane so as to be substantially similar to the array in the cross section of the composite strands after focusing, and the array is arranged. The device that focuses without breaking it and the high back tension are very effective.

FIG. 6 shows a schematic diagram of the internal structure of a composite material strand in which uncured yarns are uniformly arranged in a plane and are bundled without breaking the arrangement.

All uncured yarns in the composite strand are aligned so that they are oriented parallel to the axial direction of the composite strand.

FIG. 7 shows a schematic diagram of the internal structure of a composite material strand that is twisted and focused as in the prior art.

The uncured yarn in the composite material strand is not oriented parallel to the axial direction of the composite material strand, but has a spiral orientation.

The bundled uncured yarn 9 is coated with fibers by the coating device 5 to form the composite material strand 8. Braiding, winding, and wrapping are used for covering with fibers.

As the fibers, synthetic fibers such as polyester and vinylon are used. The composite material wire 8 is wound around the wire drum 10 by the winding device 6 after manufacturing.

When the outer circumference of the bundled uncured yarn is covered with a high shrinkage yarn having a heat shrinkage of 7 to 15%, the fiber shrinks due to heating at about 100 to 160 ° C. during heat curing,
By increasing the tightening pressure of the fiber core and giving a flow to the resin that is eluted by heating, the inside of the fiber core and the voids between the fiber core and the coating are replaced with the resin, resulting in a dense bonded fiber, resulting in a remarkable breaking strength. improves.

As such a high shrinkage yarn, a highly shrinkable polyester fiber (for example, Teijin Polyester T300S
BHT 250d), but is not limited thereto.

FIG. 9 shows the breaking load of each strand after heat-curing after twisting the polyester obtained in accordance with the method of Example 3 with respect to polyesters having various heat shrinkage rates.

According to the method for manufacturing the composite material strand described above, the steps of impregnating the high-strength fiber yarn 7 with the thermosetting resin, heating and drying them to form the uncured yarn 9, and the uncured yarn are A step of arranging them uniformly in a plane and then converging them so as to be aligned in parallel;
The process of covering the outer periphery of the fiber with a braid or the like can be configured as a continuous process, and the manufacturing process can be simplified.

Further, it is not necessary to wind the uncured yarn 9 around the bobbin during the process, and damage due to handling can be prevented, so that the strength development rate is improved.

Next, a composite material single wire using a composite material strand,
A method for manufacturing the composite stranded wire will be described. FIG. 8 is a schematic diagram of an example of a method for manufacturing a composite material single wire and a composite material stranded wire.

The composite material wire 8 unwound from the wire drum 10 is twisted by the twisting device 11.

Of course, when the final product is a single composite material wire, the twisting step is omitted and the complete curing is performed in the final curing furnace 12.

The twisting device 11 may be an ordinary wire producing device, that is, a closer or a strander.

Since the composite material wire 8 is a flexible material, it is desirable that the twist pitch be longer than that of the steel wire wire, as in general soft metal.

The twisted composite material wire 8 is the final curing furnace 1.
In 2, the impregnated uncured thermosetting resin is completely cured by heating or the like.

As a curing means other than heating, ultraviolet irradiation,
There is a method such as holding at room temperature for a long time.

If the curing temperature is not properly selected in this final curing, the thermosetting resin may leak from the fiber coating.

The composite material single wire or the composite material stranded wire 14 completely cured by the final curing furnace 12 is the product winding device 1
It is wound up by 3 and becomes a product.

[0091]

Example 1 In the first example, the number of constituent filaments is 120.
20 high-strength fiber yarns 7 of 00 PAN-based carbon fibers
It is an example manufactured using a yarn.

The thermosetting resin impregnated in the high-strength fiber yarn 7 was an epoxy resin which was solid at room temperature.

As the solvent, two kinds of mixed solvents (methyl ethyl ketone and methanol) were used. The proper mixture ratio of the solvent is methyl ethyl ketone: methanol = 35-60: 65-40.

At the time of production, a ratio of 50:50 was used in consideration of the difference in evaporation rate of both solvents. 6 phr of dicyandiamide was added as a curing agent, and 1.2 phr of DCMU was added as a curing accelerator.

The resin, the curing agent and the curing accelerator are dissolved using a mixed solvent, and the solid content concentration depends on the target fiber volume ratio, the production rate, and the temperature of the impregnating solution, but an appropriate range is 2.
It is 0% wt to 65% wt.

Manufacturing speed is 1.5 m / min. Under the above conditions, a high concentration resin can be squeezed continuously by attaching a nip roll to the impregnation tank.

Manufacturing speed 1.0 m / min. In this case, the solid content concentration is about 31% wt, and the fiber volume ratio is about 66%.

The drying conditions vary depending on the production rate, but the proper drying furnace temperature is 60 ° C. to 200 ° C., and the production rate is 1.0 m / min. In the case of 1, the residual solvent ratio becomes 1.0% wt or less when the drying furnace temperature is 70 ° C. and the residence time in the furnace is 8 minutes.

Braiding was carried out using polyester fibers for the fiber coating after bundling. Wire diameter after focusing is φ
It is 4.4.

Under the above conditions, the PAN-based carbon fiber composite material wire 8 is manufactured. The composite material wire 8 is finally cured by itself, or is finally cured after being twisted into 7, 19, 37 or the like.

The furnace temperature of the final curing furnace for the 37 composite strands 14 is about 130.degree. Depending on the curing state of the epoxy resin, it is necessary to raise the furnace temperature of the final curing furnace stepwise from a lower temperature.

The residence time in the final curing furnace is 40 min. , The production speed of the twisted wire is 0.5 m / min. Is.

[0103]

Example 2 The second example is 300 filaments.
This is an example in which 40 high-strength fiber yarns 7 of 0 pitch-based carbon fibers are manufactured.

The thermosetting resin with which the high strength fiber yarn 7 was impregnated was an epoxy resin which was solid at room temperature. Methyl cellosolve (methylene glycol monomethyl ether) was used as the solvent.

6 phr of dicyandiamide as a curing agent
In addition, 1.2 phr of DCMU is added as a curing accelerator.

The resin, the curing agent and the curing accelerator are dissolved using a solvent. The solid content concentration depends on the target fiber volume ratio, production rate and impregnating liquid temperature, but an appropriate range is 18%.
wt-60% wt.

Manufacturing speed is 2.0 m / min. Under the above conditions, a high concentration resin can be squeezed continuously by attaching a nip roll to the impregnation tank. Manufacturing speed 1.5 m / min. In the case of, the solid content concentration is about 23% wt and the fiber volume ratio is 66%.
It will be about.

The drying conditions vary depending on the production rate, but the proper drying furnace temperature is 60 ° C. to 200 ° C., and the production rate is 1.0 m / min. In this case, the residual solvent ratio becomes 1.0% wt or less when the drying furnace temperature is 91 ° C. and the residence time in the furnace is about 5 minutes.

Braiding was carried out using polyester fibers for the fiber coating after bundling. Wire diameter after focusing is φ
It is 4.4.

Under the above conditions, the pitch-based carbon fiber composite material wire 8 is manufactured. The composite material wire 8 is finally cured by itself, or is finally cured after being twisted into 7, 19, 37 or the like.

The furnace temperature of the final curing furnace for the composite twisted wire 14 of 37 strands is about 160.degree. Depending on the curing state of the epoxy resin, it is necessary to raise the furnace temperature of the final curing furnace stepwise from a lower temperature. Residence time in final curing oven is 40m
in. , The production speed of the twisted wire is 0.5 m / min. Is.

[0112]

[Comparative Example 1] As a first comparative example, the difference in the production speed between the case of individually drying the uncured yarn in units of yarn and the case of forming the fiber core by bundling is shown.

Number of PAN filaments 12000
18 high-strength fiber yarns 7 of PAN-based carbon fibers were used to impregnate an epoxy resin with a resin liquid having a solid content concentration of 40% wt diluted with methyl cellosolve to prepare an uncured yarn 9, and then a solvent was used. Was dried.

The heating and drying oven 3 is different from the ovens used in Examples 1 and 2 in the amount of drying air, but the drying oven temperature is 100 ° C.
And

Comparing the residence time in the furnace where the residual solvent ratio was 1.0% wt or less, it was found that 49 was found when a fiber core was formed.
min. Whereas it was necessary, it was 16 min. It was necessary, and the drying time could be shortened to 1/3 or less. That is, the manufacturing speed is 3
It turns out that there is more than a double difference.

[0116] Further, the fiber strength development rate of the composite material single wire 14 when dried individually in yarn units is 87% to 9%.
At 8%, the average value was 94%, and since the impregnation state was good, high strength development was facilitated.

[0117]

[Comparative Example 2] As a second comparative example, when the uncured yarn 9 is focused, the focusing position in the cross section of the composite material strand of each uncured yarn is set at a fixed position, and the uncured yarn is used as the composite material. A comparison of the tensile breaking load after final curing and its variation in the case of being bundled so as to be aligned parallel to the axial direction of the wire and in the case of being bundled by performing a twisting treatment is shown.

PAN with 12000 constituent filaments
An uncured yarn 9 was prepared by impregnating the epoxy resin into the yarn using 18 yarns of the high-strength fiber yarn 7 of carbon fiber.

At this time, for the sample to be twisted, the uncured yarn was once wound on a bobbin, twisted and bundled using a closer type twisting device to form a composite material strand 8.

The twist angles of the wires were 5 °, 10 ° and 15 °. In addition, the uncured yarns 9 are arranged almost evenly on the plane.
Samples focused so as to be aligned in parallel with each other were made into composite material strands 8 in a continuous process without being rewound on bobbins.

The breaking load of these composite material single wires 14 is
The average breaking load of the sample twisted at a twist angle of 5 ° was 3043 kgf, 1031 was 2931 kgf, and 15 ° was 2801 kgf, and the coefficient of variation of the breaking load was about 5.0%. In the sample in which the uncured yarns 9 were substantially uniformly arranged and were aligned so that the uncured yarns 9 were aligned in parallel, the average breaking load was 3060 kgf, and the variation coefficient of the breaking load was about 5.9%. The number of samples in the tensile test is 160.

As shown by the above results, even in the sample in which the composite material strands 8 were formed by concentrating so that the uncured yarns 9 are aligned in parallel and the uncured yarns 9 are aligned in parallel without the twisting process, It was found that even when the sample subjected to the twisting treatment by winding the bobbin after manufacturing the uncured yarn 9 was compared with the breaking load and its variation, there was almost no difference.

A similar strength test was carried out on a 7-strand composite material stranded wire 14, and similar results were obtained although the breaking load per composite material was slightly lowered due to the volume effect.

[0124]

[Embodiment 6] In FIG. 1, 40 bobbins each having 3000 units of pitch-based carbon fibers of 10 μ as a unit were set on the creel stand 1, and carbon fibers were continuously drawn out from each bobbin and aligned at regular intervals. In this state, the resin is continuously supplied to the impregnation tank 2 containing a thermosetting resin mainly composed of an epoxy resin for impregnation, and then continuously supplied to the drying furnace 3 and heated to 90 ° C. By skipping the solvent part of the thermosetting resin adhering to the
The carbon fiber is dried so as to be about%.

Subsequently, 40 uncured carbon fibers are continuously run, and they are converged from a parallel state without being twisted and braided into a bundle having a diameter of about 4 mmφ.

Subsequently, the uncured carbon fiber bundle is continuously supplied to the braider (coating device) 5 to obtain the high shrinkage yarn (14).
Two 250 denier Tetoron yarns that shrink 10% at 0 ° C
The outer peripheral portion of the uncured carbon fiber bundle is continuously coated with a blade thread coating material formed from a book.

The carbon fiber-reinforced thermosetting resin filaments continuously discharged from the braider were wound by a winding device.

Next, a plurality of bobbins wound with the carbon fiber reinforced thermosetting resin filaments are installed in a twisting machine, and the plurality of bobbins are continuously drawn out and twisted to form an uncured twisted wire. The carbon fiber stranded wire, which was continuously supplied to a curing furnace in an atmosphere of atmospheric pressure and cured at 140 ° C., was continuously wound by a winding machine to obtain a product.

Teijin Tetoron T300S BHT 250
Example 3 product using d, and Teijin Tetron T303
Various physical properties of the product (Comparative Example 3) obtained in the same manner as in Example 3 using K BHT 250/48 (2% shrinkage) yarn were measured, and the results shown in Table 1 were obtained.

[0130]

[Table 1]

[0131]

The improvement effect of the present invention will be shown below.

First, the effect on the production speed will be shown. As shown in the first comparative example showing the difference in the drying speed depending on the presence or absence of the fiber core formation, as compared with the case of forming the fiber core by bundling the high-strength fiber yarn, each of the yarns was dried individually. In this case, the drying time could be shortened to 1/3 or less.

That is, the manufacturing speed can be tripled or more. This effect becomes more remarkable as the number of uncured yarns forming the composite material strand increases.

Further, it has become possible to obtain tackiness that can be handled without using dry powder or the like.

Next, the effect of simplifying the manufacturing process will be described. As shown in the second comparative example above, the uncured yarns are arranged parallel to the axial direction of the composite material strand while arranging the uncured yarns at fixed positions in the cross section of the composite material strand. By concentrating so as to be aligned with each other, it was possible to manufacture a sample which was almost comparable to the sample subjected to the twisting treatment and the breaking load in a continuous process.

As a result, the manufacturing process of the composite material strand, which was largely divided into two in the conventional manufacturing method, can be unified, and the simplification can be realized.

If a high shrinkage yarn is used as a covering material for the outer periphery of the composite material, the inside of the filamentous material becomes dense and the breaking strength is also improved.

[Brief description of drawings]

FIG. 1 is a schematic plan view showing an example of a manufacturing process of a composite material strand according to the present invention.

FIG. 2 is a side view showing an example of a manufacturing process of a composite material strand according to the present invention.

FIG. 3 is a schematic view of a focusing state in which kink is prevented by the focusing device of the present invention.

FIG. 4 is a schematic diagram of a focused state in which it is difficult to prevent kinks.

FIG. 5 is a schematic diagram of a focused state in which it is difficult to prevent kinks.

FIG. 6 is a schematic diagram of an internal structure of a composite material strand according to the present invention.

FIG. 7 is a schematic diagram of an internal structure of a composite material strand according to a conventional technique.

FIG. 8 is a schematic view showing an example of a manufacturing process of a composite material single wire and a composite material stranded wire.

FIG. 9 is a view showing the strength improving effect of the high shrinkage yarn.

[Explanation of Codes] 1 Creel 2 Resin impregnation tank 2a Nip roll 3 Heating / drying furnace 4 Focusing device 5 Covering device 6 Winding device 7 High-strength fiber yarn 8 Composite material strand 9 Unhardened yarn 10 Strand drum 11 Stranding device 12 Final curing furnace 13 Product winding device 14 Composite material single wire or composite material stranded wire

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location D06M 15/19 D07B 5/00 Z (72) Inventor Mamoru Izumiyama 20-1 Shintomi, Futtsu-shi Shinnihon (72) Inventor Yasuhiro Akita 20-1 Shintomi, Futtsu-shi Nippon Steel Co., Ltd. Technical Development Headquarters (72) Inventor Yoshio Nakazawa 2-6-3 Otemachi, Chiyoda-ku, Tokyo Inside Nippon Steel Co., Ltd. (72) Inventor Ryoichi Naka 2-6-3 Otemachi, Chiyoda-ku, Tokyo Inside Nippon Steel Co., Ltd. (72) Teruo Iwashita 1618 Ida, Nakahara-ku, Kawasaki City New Nippon Steel (72) Inventor Shingo Shibamoto, No. 1 Fuji-machi, Hirohata-ku, Himeji City Nippon Steel Co., Ltd. Inside the Hirohata Works (72) Inventor, Yuji Goto Fuji-machi, Hirohata-ku, Himeji-shi Address Inside Nippon Steel Co., Ltd. Hirohata Works (72) Inventor Mikio Shima 15-1 Shinko, Kisarazu City, Chiba Prefecture Nippon Steel Chemical Co., Ltd. Product Development Center (72) Inventor Yasuji Sato Kisarazu, Chiba Prefecture 15-1 Shinko City, Nippon Steel Chemicals Co., Ltd. Product Development Center (72) Inventor Hideki Komori 7-5-1 Higashi Narashino, Narashino City, Chiba Prefecture (5-2) Inventor, Kaji Endo Kaji Higashi, Narashino City, Chiba Prefecture Narashino 7-5-1 Suzuki Metal Industry Co., Ltd. (72) Inventor Atsushi Morii Higashi Narashino 7-5-1, Narashino City, Chiba Prefecture (72) Inventor Yoshihiro Abe 7-5 Higashi Narashino, Narashino City, Chiba Prefecture ―1 Suzuki Metal Industry Co., Ltd.

Claims (10)

[Claims] 1. A plurality of high-strength fiber yarns such as carbon fiber, glass fiber and aramid fiber are run under constant tension, impregnated with thermosetting resin in each yarn unit, and further dried in a heating furnace in each yarn unit. When a plurality of uncured yarns are bundled into a composite material strand by processing, the uncured yarns are placed at a fixed position in the cross section of the composite material strand. Meanwhile, a method for producing a composite material, in which uncured yarns are bundled so as to be aligned parallel to the axial direction of a composite material strand, and the outer periphery of the bundled uncured yarns is covered with fibers such as a braid. 2. A step of running a plurality of high-strength fiber yarns such as carbon fiber, glass fiber, and aramid fiber under a constant tension, impregnating each yarn unit with a thermosetting resin, and heating and drying them to obtain an uncured fiber. In the process of forming the yarn, when the multiple uncured yarns are bundled into a composite material strand, the uncured yarns are arranged while the focusing position of each uncured yarn in the cross section of the composite material strand is fixed. As a continuous process, the entire process of manufacturing composite material strands consists of the steps of bundling so that they are aligned parallel to the axial direction of the composite material strands, and the step of covering the outer periphery of the bundled uncured yarn with a braid or the like with fibers. A method for manufacturing a composite material strand, characterized in that it is configured. 3. A composite material single wire produced by curing the impregnated thermosetting resin by a method such as heating the composite material strand manufactured by the manufacturing method according to claim 1 or claim 2 alone. Manufacturing method. 4. The composite material strands produced by the production method according to claim 1 or 2 are twisted together, and then the impregnated thermosetting resin is cured by a method such as heating. Manufacturing method of composite stranded wire. 5. A composite material wire produced by bundling a plurality of uncured yarns impregnated with a thermosetting resin for each of a plurality of high-strength fiber yarns such as carbon fiber, glass fiber, aramid fiber, etc. Align the uncured yarns in the cross-section of the material strands so that the uncured yarns are focused and the high-strength fibers in all uncured yarns in the composite strands are oriented parallel to the axial direction of the composite strands. A composite material strand characterized in that 6. A composite material single wire produced by curing the impregnated thermosetting resin by a method such as heating the composite material wire of claim 5 alone. 7. A composite material twisted wire produced by twisting a plurality of the composite material wires according to claim 5 and then curing the impregnated thermosetting resin by a method such as heating. 8. A plurality of high-strength fiber yarns such as carbon fiber, glass fiber, and aramid fiber are run under constant tension, impregnated with a thermosetting resin for each yarn unit, and further dried in a heating furnace for each yarn unit. When a plurality of uncured yarns are bundled into a composite material strand by processing, the uncured yarns are placed at fixed positions in the cross section of the composite strand. Meanwhile, the uncured yarns are bundled so as to be aligned parallel to the axial direction of the composite material strands, and the outer periphery of the bundled uncured yarns is covered with a fiber having a heat shrinkage ratio of 7 to 15%, such as a braid, etc. Wire manufacturing method. 9. The heat treatment temperature during heat curing is 100 to 160.
9. The method according to claim 8, which is in ° C. 10. A plurality of high-strength fiber yarns such as carbon fiber, glass fiber, and aramid fiber are run under constant tension,
Each yarn unit is impregnated with a thermosetting resin, and each yarn unit is dried in a heating furnace to form an uncured yarn.
When a plurality of uncured yarns are bundled to form a composite material strand, the uncured yarns are made into composite material strands while the focusing position of each uncured yarn is set at a fixed position in the cross section of the composite material strand. The filaments are bundled so as to be aligned in parallel to the axial direction of the, and the outer circumference of the bundled uncured yarn is covered with a fiber having a heat shrinkage ratio of 7 to 15%, such as a braid, to form a composite material strand. A method for producing a filamentous article of a composite material, which comprises twisting or not twisting, and then thermosetting a thermosetting resin at 100 to 160 ° C. and shrinking the coated fiber.