JPH0321639A - Production of hot-pressed material reinforced with liquid crystal fiber - Google Patents

Abstract

PURPOSE:To stably obtain the subject hot-pressed material having high strength an modulus and stable quality and useful as hightenacity fiber, etc., by forming a conjugate fiber from a liquid crystal resin and other resin, collecting the fibers and hotpressing the collected bundle at a temperature above a specific level. CONSTITUTION:The objective hot-pressed material can be produced by carrying out conjugate spinning of (A) a liquid crystal resin as the 1st resin and (B) a second resin, collecting obtained conjugate fibers and hot-pressing the collected fiber aggregate at a temperature above the softening point of the component B. It is preferable to carry out the hot-pressing at or above the softening point of the component B after heat-treatment of the collected fiber aggregate at >=(Tm-10 deg.C) (Tm is melting point of the component A) and the component A is preferably a resin having a melting point higher than that of the component B by 10 deg.C, especially a liquid crystal polyester or a liquid crystal polyester amide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a thermocompression bonded article reinforced with liquid crystal fibers. Furthermore, in detail, it relates to a method for producing thermocompression bonded products reinforced with liquid crystal plow fibers obtained by thermally fusing fibers arranged in one direction. [Prior Art] So-called FRP, which uses glass fiber, carbon fiber, or the like as a reinforcing material, is widely used.

However, such molded products had the following drawbacks.

That is. ■It's heavy when you look at it as an object. ■Since the reinforcing fibers cannot be well colored, the obtained FR
P has poor aesthetics.

■Especially when used in the electrical field, it has a high dielectric constant or
They often have high conductivity, which limits their field of use.

■Because the ratio of reinforcing fibers and resin may differ locally, physical properties may not be stabilized.

For this reason, its uses were limited. On the other hand, in terms of process, (1) the fibers are often destroyed during the process of forming glass fibers, carbon fibers, etc. into the desired shape, resulting in unstable physical properties. ■Especially when adding glass fibers, carbon fibers, etc. to polymers as reinforcement materials. The reinforcing fibers damage the screws and cylinders of the extruder, forcing them to be replaced periodically, resulting in high costs.

■It is not easy to uniformly mix reinforcing fibers and resin (apply resin to fibers), etc. For this reason, the physical properties of the obtained molded product were not stabilized, and the cost was high. However, such problems are considered to be essential problems when using glass fibers, carbon fibers, etc. as reinforcing materials, and currently no efforts have been made to specifically solve them.

Note that, although Japanese Patent Publication No. 61-56350 describes fibers using polyethylene terephthalate as a reinforcing material, this publication only uses polyethylene terephthalate as a reinforcing material, and this is not the purpose of the present invention. belongs to.

[Problem to be solved by the invention]

The object of the present invention is to provide a method for producing composite materials that overcomes the above-mentioned drawbacks.

[Means to solve the problem]

In view of this current situation, the inventors of the present invention have arrived at the present invention as a result of extensive studies without being bound by conventional research concepts. The present invention aims to solve the above problems. It has the following configuration.

(11 ■ Step of thermocompression bonding the liquid crystal resin, which is the first resin, and the second resin; [2] Step of converging the composite fibers; ■ Step of converging the composite fibers at a temperature higher than the softening point of the second resin; A method for producing a thermocompression bonded product reinforced with liquid crystal fibers, which comprises a process of thermocompression bonding of fiber collection and eight combinations.

(2) ■ Step of thermocompression bonding the liquid crystal resin, which is the first resin, and the second resin; [2] Step of converging the composite fibers. (melting point -100) of the first resin.
A method for manufacturing a thermocompression bonded product reinforced with liquid crystal fibers, characterized by the step of heat treating the fiber aggregate at a temperature higher than the softening point of the first resin. A method for manufacturing a kimono. (3) The melting point of the first resin is 10% lower than the melting point of the second resin.
A method for producing a thermocompression bonded product reinforced with liquid crystal fibers according to 1 or 2, using a resin with a temperature higher than ℃. (4) The first liquid crystal resin is
A method for producing a thermocompression bonded article reinforced with the liquid crystal fiber according to any one of 1 to 3, which is a liquid crystal polyester or a liquid crystal polyester amide. (5) The second resin is a non-liquid crystal resin.
A method for producing a thermocompression bonded article reinforced with liquid crystal fibers according to any one of items 1 to 3. (6) Any one of 1 to 3.5, wherein the second resin is a liquid crystal resin and has a lower melting point than the first resin, or a liquid crystal resin whose melting point increases at a lower rate when subjected to high-temperature heat treatment. A method for producing a thermocompression bonded article reinforced with liquid crystal fibers as described above.

(7) The method for producing a thermocompression bonded product reinforced with liquid crystal fibers according to 1 or 2, wherein the thermocompression bonding method is either method A or B below.

A. Melting the first resin and the second resin separately and then merging them together so that the first resin continuously forms at least one island in the second resin. Method of merging and spinning. B. A method of mixing and spinning a first resin and a second resin.

(8) Heat treatment of ljli fibers. 2. The method for producing a thermocompression bonded product reinforced with liquid crystal fibers according to 2, which is treated in an inert gas or vacuum. (9) The number average molecular weight of the liquid crystal resin that is the first resin is.
A method for producing a thermocompression bonded article reinforced with liquid crystal fiber according to any one of 1 to 4.7, which is heat-treated until the fiber becomes 30,000 or more.

1 to 4, heat treatment until the melting point of the liquid crystal resin, which is the first resin of α, becomes 20°C or more higher than the melting point of the second resin;
7.9. Method for producing a thermocompression bonded product reinforced with liquid crystal fibers according to any one of 7.9. (11) Thermocompression bonding of fiber aggregates is performed with rollers1
or 2. The method for producing a thermocompression bonded product reinforced with liquid crystal fibers according to 2.

(l2) The roller is a grooved roller1. 2.
12. A method for producing a thermocompression bonded product reinforced with liquid crystal fibers according to any one of Item 11.

(13) The thermocompression bonded material reinforced with liquid crystal fibers is
A method for producing a thermocompression bonded article reinforced with liquid crystal fibers according to any one of 1 to 12. A. rod. B. Gut, C.
．． Plate (14) A method for producing a thermocompression bonded product reinforced with liquid crystal fibers, characterized in that the thermocompression bonded product is cut into chips. (15) A method for producing a thermocompression bonded product reinforced with liquid crystal fibers, characterized in that the thermocompression bonded product is heat-treated at a temperature of (melting point -100)C or higher of the first resin. The present invention will be explained in further detail below.

According to the present invention, it is possible to easily, at low cost, and with high strength reinforced with liquid crystal fiber of high quality and stable quality.
It is truly amazing that it is possible to make thermocompressed products that are lightweight and have good surface quality. First, the liquid crystal resin, which is the first resin of the present invention, will be described.

The first resin in the present invention is a thermoplastic liquid crystal resin having a mesogen group in its main chain.

There are various types of such main chain type liquid crystal resins. There are no particular limitations, and conventionally known methods can be widely used. Particularly preferred liquid crystal resins include those made of aromatic polyester and those made of aromatic polyester amide. There are various types of aromatic polyesters, and conventionally known ones can be used without any particular limitation.

and. Particularly preferable ones are: Main chain type liquid crystal resins consisting of the following structural units are mentioned.

That is, here, X represents hydrogen, halogen, or an alkyl group having 4 or less carbon atoms. Here, Σni=100 in each structural formula. Particularly preferred is that ni of each structural formula is 4 or more. Also. Various substituents including halogen etc. may be added to each formula.

These materials have high melt formability and high strength. Furthermore, it has a high melting point and a high glass transition point, making it particularly preferable.

Next, there are various types of main chain type liquid crystal resins made of aromatic polyesteramide, and conventionally known ones can be widely applied, and there are no particular limitations. and. Particularly preferred are main chain type liquid crystal resins consisting of the following structural units.

Here, X represents hydrogen, halogen, or an alkyl group having 4 or less carbon atoms. Here. X is hydrogen or halogen. Represents an alkyl group with 4 or less carbon atoms. Here, Σni=100 in each structural formula. and. Particularly preferably, ni of each structural formula is 15 or more. Furthermore, various substituents such as halogen and the like may be added to each formula. These materials have melt moldability similar to main chain type liquid crystal resins made of polyester, and have high strength.

In the present invention, such a liquid crystal resin serves as the first resin.

Next, the second resin referred to in the present invention refers to a thermoplastic resin like the first resin, and conventionally known resins can be widely applied, and the second resin is not particularly limited.

Namely, polypropylene, nylon 6, nylon 66. Various nylons including nylon 6T, nylon 6/66/6T, nylon 12, etc., and general-purpose resins including polyethylene terephthalate, polybutylene terephthalate, etc. Also included are so-called general-purpose engineering plastics made of polycarbonate, polyethylene naphthalate, polyphenylene oxide and/or its modified products, polyacecool, etc. Furthermore, polyphenylene sulfide. Various aromatic etherketone resins including polyphenylene sulfide ketone, polyphenylene sulfide sulfone, and polyether ether ketone. Further examples include high-performance Embra resins including various thermoplastic fluororesins. Also, poly 1, 4
Also included are polyesters such as cyclohexane dimethylene terephthalate and/or copolymers thereof. Naturally, thermoplastic liquid crystal resins can also be mentioned.

In addition, when a thermoplastic liquid crystal resin is used as the second resin, it is preferable to have a lower melting point than the first liquid crystal resin, or to have a lower melting point increase rate when subjected to high-temperature heat treatment. The melting point of liquid crystal resins containing polyethylene terephthalate in the main chain is difficult to increase due to high-temperature heat treatment. A particularly preferred second resin is a liquid crystal resin.

Although the composite fiber obtained by the present invention requires the above-mentioned precautions, other polymers and plasticizers may not be added to the extent that they do not impede the effects of the invention. Lightfast agent. Antistatic agent. Terminal stopper, fluorescent whitening agent. Flame retardants. Antiaging agents and the like may also be contained. Also, titanium oxide. Inorganic substances such as iron oxide and carbon blank may also be contained.

In the present invention, a thermocompression bonded article is produced in which the first resin is reinforced with liquid crystal fibers so that the reinforcing fibers of the second resin become the reinforcing fibers.

That is, in the present invention, (1) the liquid crystal resin, which is the first resin, and the second resin are bonded together by thermocompression. Next, [2] the composite fibers are converged. Furthermore, after that, the fiber aggregate is bonded under heat at a temperature above the softening point of the second resin. Also, if necessary, [
2] after the convergence process. As step (2), (1) the converged conjugate fibers are heated to a temperature higher than (melting point -100)"C of the first resin,
Added heat treatment (steps 2 and 3 can be reversed).
The fiber aggregate is then thermally fused at a temperature above the softening point of the second resin. Thermocompression bonding in the present invention refers to a spinning method in which two or more types of bolamers are simultaneously discharged from the same hole of a spinneret. That is,
So-called core-and-sheath type, bimetallic type, polymer array type with multiple cores, and blend spinning method. Typical examples include a split peel type, a micro split type with a large number of split peels, a hollow polymer array type, and a hollow split peel type.

Among these spinning methods, a particularly preferred method is one in which the liquid crystal resin component is continuous within the fiber. Furthermore, a spinning method in which the first resin, the liquid crystal resin, is covered with the second resin and then discharged is preferable. That is, the core-one-sheath type, and the so-called polymer array type, in which many islands are dispersed within a matrix volima. is particularly preferred.

Both the first resin and the second resin are continuous within the composite fiber. It is particularly preferable that the first resin is fibrous in the second resin. The fibrous material is continuous within the second resin. and,
Particularly preferably, there are three or more such fibrous materials per 1000 square microns of the cross section of the composite fiber.

More preferably 5 or more. More preferably, ten or more fibrous materials are present in the composite fiber. As the number increases, the properties of the resulting iron fibers become more stable. Also,
Impact resistance is also improved. Furthermore, flexibility is improved. It becomes difficult to fibrillate.

It is also preferable that the thickness of the first resin is not too thick. The diameter of the particularly preferable fibrous first resin is 20 μm or less. More preferably 10μ or less. Particularly preferred is 5μ or less. When the diameter of the first resin is reduced, not only the strength of the resin composite is increased, but also the surface of the resin composite is particularly good. Also. In particular, impact strength increases. Furthermore, since the degree of crosslinking between the first resin and the second resin may also increase, peeling or the like is less likely to occur at the interface between the two. In other words, it becomes a composite plow fiber with high fibril resistance. Moreover, the physical properties become stable. Thus, although the reason for this is unclear when the spinning method of the present invention is used, It offers the following major advantages.

■From a methodological point of view (a), if we take such precautions. For some reason, the spinning is stable and can be spun at higher speeds than when spinning liquid crystal resin alone. For this reason. Productivity improves. (b) A second resin that is difficult to spin can be spun.

Moreover. It can be spun at a higher speed than the second resin alone.

■From things (a) Thin fibers made of liquid crystal resin are produced.

(Note) A large number of liquid crystal resin fibers can be created in the second resin. (C) The ratio of the first resin and the second resin is constant.

(2) Higher strength than fibers obtained by spinning liquid crystal resin alone. Fibers with high elastic modulus can be obtained. It is preferable that the spinning speed when performing such thermocompression bonding is high. If it is fast, the orientation of the liquid crystal resin will progress. preferable. The preferable spinning speed is 500 m/min or more, more preferably 1000 m/min or more, and still more preferably 2000 m/min or more. In this way, the first resin becomes highly oriented and becomes a high-strength fiber. In this plow fiber spinning process. Appropriately, apply a magnetic field, electric field, microwave, or heat the bottom of the mouthpiece. Even if you create a vacuum under the cap. I don't care.

Next is the ratio of the first resin and the second resin. The proportion of the first resin is preferably 5% by weight or more. If it is less than 5% by weight, the effect of reinforcing the second resin is low, which is not preferable. Furthermore, if the first resin exceeds 97% by weight, the spinnability and handling properties of the composite fiber often deteriorate, so it is preferable that the maximum ratio of the first resin is 97% by weight or less. Than. The preferred ratio is 10% to 6% by weight of the first resin.
It is 0% by weight.

Next, the combination of the first resin and the second resin is determined by their compatibility, reactivity during melting, and melting point. It should be determined taking into consideration the thermal decomposition point, etc.

In this combination, it is preferable that the first resin has a melting point of . It is higher than that of the second resin. More preferably, the temperature difference is 10°C or more, and more preferably 20°C or more.
The temperature must be at least ℃. or. The key is to select a resin whose melting point difference increases with high-temperature heat treatment. It is preferable that the difference in melting point between the two is 10°C or more because it facilitates the thermocompression bonding process. Further, the fineness of the composite fiber of the present invention is not particularly limited. A wide range of woven fibers with known fineness can be used.

Next, the fibers thus obtained are condensed to a predetermined thickness (thickness, width). In addition. Convergence may be performed continuously or simultaneously with the spinning process. The convergence method is not limited, and conventionally known methods can be applied. In addition.
In the spinning and convergence process. When using an oil agent, it is essential that it does not impair the physical properties after heat fusion, so it is important to consider the combination with the resin when using it. Also, using a good oil can make the next step of heat treatment easier. The selection of the oil to be used is extremely important. Next, the converged fiber aggregate is heated to a temperature above the softening point of the second resin. Heat and press. Conventionally known methods can be widely applied to thermocompression bonding. It is not limited in any way.
That is. The thermocompression bonding may be carried out continuously using a heating roller, or it is preferable to heat the material in a heating furnace and then thermocompression bonding using a roller. Alternatively, a method such as flat plate pressing may be used. Also,
So-called. You can also use the dice method. That is, it is a method in which the converged fiber aggregate is passed through narrow holes or slits and bonded under heat. And as a method of thermocompression bonding. Particularly preferred is continuous thermocompression bonding using a roller. Since it can be done continuously, it has the great advantage of reducing costs. Also. Particularly preferred as rollers are grooved rollers. A grooved roller allows for even adhesion. Various preferred grooved rollers are shown in Figures 1-7. It is also preferable to carry out thermocompression bonding using multistage rollers as shown in FIGS. 6 and 7. Also. A slit part (fiber convergence device) fixed to a roller as shown in Figures 8 to 9
It is also preferable to provide. It is also a preferable method to attach a convergence tool in front of the groove. next. The atmosphere for thermocompression bonding may be air, sealed with an inert gas such as nitrogen, or carried out in a vacuum or under reduced pressure. That is. A portion of the roller may form a sealed structure as a whole. Additionally, a preheating device (furnace) or the like may be installed in front of a portion of the roller. Additionally, a magnetic field, electric field, microwave, etc. may be applied during thermocompression bonding. By doing so, it is possible to stably obtain a thermocompression bonded product reinforced with liquid crystal fibers.

And especially when you want a high-strength thermal adhesive. When it is desired to facilitate the thermocompression bonding process, the converged fiber aggregate is heated to a melting point of -10 of the first resin of the composite fibers before thermocompression bonding.
The heat treatment is preferably performed at a temperature of 0)'C or higher. Note that this heat treatment is carried out after the composite fiber is spun, that is. It may be performed before convergence. There is no problem with heat treatment even in air as long as the second resin has excellent high temperature resistance such as polyphenylene sulfide or various aromatic polyether ketones.

However, it is particularly preferable to carry out the reaction under a flow of an inert gas such as nitrogen or under vacuum.

Particularly preferably, the treatment is carried out at a high temperature of (melting point -50)C or higher of the first resin. This increases the melting point of the first resin. In addition, depending on the time, it often becomes infusible. Furthermore, there is a significant effect that the strength of the first resin is significantly increased. Also. Depending on the type of the first and second resins, crosslinking may occur between the first and second resins, improving fibril resistance. And especially. If you want to shorten this high temperature treatment time, add an alkali metal salt or alkaline earth metal salt to 0.05ffi amount % to 5N based on the weight of the first resin! It is preferable to contain and/or adhere to at least 1% of the second resin and to perform high temperature treatment. By doing so, the high-temperature heat treatment time can be reduced to less than half that of treatment without additives.

In addition, such salt may be added at the time of melting. Further, it may be applied after forming the composite fiber. In particular, when the salt is an organic salt, it is preferably added later as a composite fiber.

In addition, especially when it is preferable that the first resin in the composite fiber is infusible. It is preferable to carry out such high-temperature heat treatment and further treat the resin composite at a high temperature. That is, it is preferable to process at a temperature higher than the melting point of the first resin. In addition. The melting point of the first resin increases with heat treatment. High? E.
It is necessary to carry out heat treatment while checking the melting point of the first resin after heat treatment.

This allows the first resin to become infusible within the composite fiber. Whether or not the first resin has become infusible can be easily confirmed by measuring the liquid crystal resin composite with a differential scanning calorimeter (DSC). In addition, due to such heat treatment. It is preferable to heat-treat the first resin until the number average molecular weight becomes 30,000 or more. In this way, strength and elastic modulus. Both elongation increases. Therefore, the strength of the resin composite. It is preferable because the elastic modulus is also high.

Also, the melting point of the first resin is 10°C higher than the melting point of the second resin.
It is preferable to perform heat treatment until the temperature becomes higher than that. By doing this. The heat resistance of thermocompressed products reinforced with liquid crystal fibers is improved. Also, its strength will increase. It also makes the next process of thermocompression bonding easier. Particularly preferred.

Thereafter, the fiber aggregate is thermocompressed by the method described above.

The shape of the thermocompressed product thus obtained depends on its shape. Can be made into various things. In other words, it can be made into rods, guts, and even plates. Furthermore, if you cut it, you can make it into chips.

Furthermore, when it is desired to further improve the strength of the thermocompression bonded product, it is also effective to further heat treat the thermocompression bonded product. As the heat treatment method, the above-mentioned method can be used.

The thermocompression bonded product reinforced with the liquid crystal fiber of the present invention has high strength and... Excellent impact resistance and fibril resistance. Also, since the surface can be made well, it can be used in many fields. An example is shown below. High-strength fibers, reinforcing materials, reinforcing materials for optical fibers. Materials for propellers, window frames, blinds, and parabolic antennas. Weatherproof reinforcement materials, sinks, kitchen utensils, system kitchens, concrete reinforcement materials, marine concrete reinforcement materials, marine materials, helmets, molding chips. Chimp for high strength molding. Injection molding tips, vaulting bars, skis, fishing rods, and various bars.
Surveying bar. Support rod for equipment for iiiJ quantity. FRP, F
Base material for RP, base material for electrical insulation, base material for printed circuit boards, lobes, protective materials. Screen gauze, filters, reinforcing materials for filters, base materials for yarns mixed with carbon fiber, etc., high-strength film materials, military materials, roofing materials, tents. Temporary roofing materials, wall materials, desks, plywood facing materials, high-strength cloth, and various frames.
Bicycle base materials, superconducting materials, paper making. Shear fabrics for printing, etc., detent stars, sliding parts. Frames for various electrical equipment, such as low-shrinkage heat-sealing materials, laundry rods, aircraft materials, wall materials for aircraft cabins, dashboard base materials, wood reinforcement materials, etc. Handles, instrument panel equipment, bags, cases, fountain pen base materials. Mechanical pencil base materials, drafting tools, rulers, eyeglass frames, eyeglass frames, etc. This will be explained in more detail below using examples.

It goes without saying that the present invention is not limited to these embodiments.

[Example] Example 1 As shown below, the main chain type liquid crystal resin, which is the first resin, was
A liquid crystal resin composite consisting of polymer array fibers containing a second resin, polyphenylene sulfide, was produced.

There were no particular problems with yarn reeling.

A. Silk spinning conditions ■Shima Kaibun (first resin): Liquid crystal resin Vectra A950 manufactured by Hoechst Celanese, USA ■Sea component (second resin): Polyphenylene sulfide manufactured by Toray Phillips Petroleum ■Shima/Sea-30 /70 (weight ratio) ■ Number of islands - 70 ■ Spinning temperature - 305°C ■ Spinning speed - 1500 m/min ■ Stretching ratio - None.

B. Characteristics of the obtained fiber ■ Fineness of liquid crystal resin composite = 30 denier (hereinafter referred to as d) ■ Strength - 4 g/d ■ Elongation = 1.8% ■ Elastic modulus - 190 g/d Next, the plow fiber was The material was converged to a density of 1,000,000 denier, passed through a heating furnace heated to 290°C, and then hot pressed using a grooved roller heated to 270°C as shown in Fig. 5 to form a thermocompressed gut. Continue. It was cut with a cutter to obtain a chip approximately 10 cm in length. There were no particular problems with the process. Next, the chips were treated in a nitrogen stream at 250°C for 1 hour, and then in a nitrogen stream at 270°C for 5 hours. Next, when the chip was passed through an extruder and formed into a plate, it was formed well. The strength of this board is approximately 12 times higher than the bending strength of a similar plate made of Kaikaibu PPS alone, and the impact strength is approximately 2 times higher.
It was 0 times stronger.

In addition. DSC revealed that the melting point of the first resin of Chimp heat treated in a high temperature nitrogen stream was 325°C, and the melting point of the second resin was 285°C. In addition, Vectra before spinning. The melting point of both polyphenylene sulfides is approximately 285.
It was ℃. That is. The melting point of the first resin was increased by about 40°C due to the heat treatment.

Example 2 The fiber of Example 1 was wound around a perforated pirn and heated at 250°C for 1 hour and at 270°C for 3 hours while nitrogen was flowing from inside. Heat treated. Next, the fibers were ground to 50,000 denier and treated in the same manner as in Example 1. Despite the large fineness, it was successfully made into chips. Example 3 By the following method. First resin. A second resin was prototyped.

Both were thermoplastic liquid crystal resins.

The melting point of the first resin is 287°C. The second resin was 256.

A. First Method for Producing Liquid Crystal Resin A polymer having the following structural formula consisting of p-hydroxybenzoic acid and 6-oxy-2-naphthoic acid was polymerized according to Japanese Patent Publication No. 3888/1988. The melting point of this polymer was 283°C. B. A polymer having the following structure consisting of p-hydroxybenzoic acid and polyethylene terephthalate was polymerized according to Japanese Patent Publication No. 18016/1983 for the production of the second resin (liquid crystal resin).The melting point of the polymer was 256°C.Next, A polymer array fiber was prepared in the same manner as in Example 1 using the above first resin as Shimabo and the second resin as Seabed. C. Silk spinning conditions Island/Sea - 30/70 ( Weight ratio) ■Number of islands = 70 ■Spinning temperature - 310°C ■Spinning speed - 600 m/min ■Stretching ratio = None.

B. Characteristics of the obtained fiber ■ Fineness of liquid crystal resin composite = 25 denier (hereinafter referred to as d) ■ Strength = 7 g / d ■ Elongation = 1.7% ■ Elastic modulus = 410 g / d Next, the fiber was It was treated in a nitrogen stream at 250°C for 1 hour, and then for 5 hours in a nitrogen stream at 250°C. The melting points of the plow fibers were 264°C for the sea component and 310°C for the island component. Next, the fibers were converged to 30,000 denier. It was passed through a heating furnace heated to 280° C., and then hot pressed with a grooved roller heated to 260° C. as shown in FIG. 5 to form a hot-pressed gut. Continue. Cut it with a cutter. Length approximately iQc
It was set as a chip of m. There were no particular problems with the process.

Next, the chip was passed through an extruder and formed into a plate, and the shape was good. What is the strength of this board? The bending strength was approximately 5 times higher than that of a plate made of only the second resin of Kaikaibun, and the impact strength was approximately 17 times higher. Also, compared to the first plate made only of resin, its warp. The horizontal strength balance is less than 1/3. It had an extremely uniform strength balance.

Example 4 According to Japanese Patent Publication No. 61-13485, the melting point of the following structure 2 consisting of 6-hydroxy-2-naphthoic acid, terephthalic acid and p-aminophenol was 284°C. Next, the resin was made into an island part, and the second resin of Example 3 was used for the seabed part. Hereinafter, the melting point of the am fiber, which was spun in the same manner as in Example 3, and subsequently treated in a nitrogen stream at 240°C for 1 hour, and further treated in a nitrogen stream at 250°C for 5 hours, was 264°C for the seabed portion. The temperature at Shimaoi was 334 degrees Celsius.
next. The following is the same as in Example 3. When we prototyped a board, we obtained a board with high strength, high impact resistance, and little difference in strength between warp and warp.

[Effects of the Invention] By taking the precautions of the present invention, the following great effects can be brought about.

■Thermocompression bonded products with high strength and high modulus of elasticity can be stably obtained. ■Produces thermocompressed products with stable quality. ■Since the liquid crystal resin composite itself is made of FRP, there is no need to add a matrix polymer afterwards. Therefore, there is no unevenness in addition. For this reason. FRP with stable physical properties can be made. This is particularly good for polymer arrays. ■The main liquid crystal resin can be made infusible. It is especially easy to mold the resin composite into chips or fibers.

[Brief explanation of drawings]

FIGS. 1 to 9 are representative views of grooved rollers used when making thermocompression bonded products reinforced with liquid crystal fibers. In Figure 1, the shape of the groove is rectangular. FIG. 2 shows an example in which the groove has a triangular shape. FIG. 3 shows an example of three grooves. Figure 4 shows an example where both rollers have grooves. Figure 5 shows an example in which a large number of grooved rollers (four rollers) are used to maintain a uniform distance between the rollers. The above figures 1 to 5 are front views of the grooved roller. Fig. 6 is a side view of the grooved roller of the multi-stage roller. Figure 7 is a side view of an example of a combination of multistage rollers and a nimp belt. Moreover, FIG. 8 is a front view of an example in which two trumpet-shaped convergence tools are installed on a roller, and FIG. 9 is a side view thereof. 1.2, 4.57 Roller 3: Groove 6: Nip belt 7: Slit 8: Fixed convergence tool for converging fibers

Claims (15)

[Claims] (1) [1] Process of composite spinning the liquid crystal resin as the first resin and the second resin, [2] Process of converging the composite fibers, [3] Convergence at or above the softening point of the second resin. 1. A method for producing a thermocompression bonded article reinforced with liquid crystal fibers, the method comprising the step of thermocompression bonding the fiber aggregates. (2) [1] A process of composite spinning a liquid crystal resin as a first resin and a second resin, [2] A process of converging the composite fibers, [3] A process of converging the converged fiber aggregate into the first resin. The step of heat-treating the resin at (melting point -100)℃ or above (steps 2 and 3)
[4] A method for producing a thermocompression bonded article reinforced with liquid crystal fibers, which comprises the step of thermocompression bonding a fiber aggregate converged at a temperature equal to or higher than the softening point of a second resin. (3) The melting point of the first resin is 10% lower than the melting point of the second resin.
3. The method for producing a thermocompression bonded article reinforced with liquid crystal fibers according to claim 1 or 2, which uses a resin having a temperature higher than .degree. (4) The method for producing a thermocompression bonded article reinforced with liquid crystal fibers according to any one of claims 1 to 3, wherein the first liquid crystal resin is a liquid crystal polyester or a liquid crystal polyester amide. (5) Claims 1 to 3, wherein the second resin is a non-liquid crystal resin.
A method for producing a thermocompression bonded article reinforced with liquid crystal fibers according to any one of the above. (6) Claims 1 to 3, wherein the second resin is a liquid crystal resin and has a lower melting point than the first resin, or a liquid crystal resin whose melting point increases at a lower rate when subjected to high-temperature heat treatment;
5. A method for producing a thermocompression bonded article reinforced with liquid crystal fibers according to any one of 5. (7) The method for producing a thermocompressed product reinforced with liquid crystal fibers according to claim 1 or 2, wherein the composite spinning method is one of methods A and B below. A. Melting the first resin and the second resin separately and then merging them together so that the first resin continuously forms at least one island in the second resin. A method of merging and spinning. B. A method of mixing and spinning the first resin and the second resin. (8) The method for producing a thermocompression bonded product reinforced with liquid crystal fibers according to claim 2, wherein the heat treatment of the fibers is carried out in an inert gas or vacuum. (9) The number average molecular weight of the liquid crystal resin that is the first resin is
8. The method for producing a thermocompression bonded article reinforced with liquid crystal fibers according to any one of claims 1 to 4 and 7, wherein the thermocompression bonded article is heat-treated to a temperature of 30,000 or more. (10) The liquid crystal fiber reinforced with the liquid crystal fiber according to any one of claims 1 to 4, 7, and 9 is heat-treated until the melting point of the liquid crystal resin as the first resin becomes 20°C or more higher than the melting point of the second resin. A manufacturing method for heat-pressed products. (11) The method for producing a thermocompression bonded product reinforced with liquid crystal fibers according to claim 1 or 2, wherein the thermocompression bonding of the fiber aggregate is performed using a roller. (12) Claims 1 and 2, wherein the roller is a grooved roller.
12. A method for producing a thermocompression bonded product reinforced with liquid crystal fibers according to any one of Item 11. (13) The thermocompression bonded material reinforced with liquid crystal fibers is
A method for producing a thermocompression bonded article reinforced with liquid crystal fibers according to any one of claims 1 to 12. A, rod, B, gut, C, board (14) A method for producing a thermocompression bonded product reinforced with liquid crystal fibers, which comprises cutting the thermocompression bonded product into chips. (15) A method for producing a thermocompression bonded article reinforced with liquid crystal fibers, which comprises heat-treating the thermocompression bonded article at a temperature of (melting point -100)C or higher of the first resin.