JPH0580341B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a composite and a method for manufacturing the same, and more particularly to a composite comprising long fibers and a film and having a curved surface at least in part, and a method for manufacturing the same. (Prior Art) With the progress of science and industry in recent years, it has become common for conventional materials used in various fields to have insufficient physical properties and not be able to exhibit satisfactory functions. For example, in aircraft, it is required to improve the strength and elastic modulus per weight of materials, and in the field of space equipment,
In order to reduce costs, it is desired to develop materials with high specific strength and specific modulus. Furthermore, when making the outer panel of an automobile from plastic in order to reduce its weight, a highly rigid plastic material is required. On the other hand, recent developments in fiber technology have led to the development of fibers with greater strength per weight and elastic modulus than iron. For example, inorganic fibers such as carbon fibers, SiC fibers, and boron fibers, para-based wholly aromatic polyamide fibers (e.g., Dupont: Kepler), fully aromatic polyetheramide fibers (Teijin: Technora), and high-density polyethylene fibers (e.g., Mitsui Petrochemicals: Techmilon) and other organic fibers. Methods such as hardening such high-performance fibers with resin to create new materials, or adding these fibers to existing resins or metals to reinforce them have been considered, and some of them have been put into practical use. For example, FRP (Fiber Reinforced
Plastic), FRM (Fiber Reinforced Metal), and CC (Carbon-Carbon) composites. Theoretically, long fibers have a better reinforcing effect as a composite material than short fibers. Therefore, in the case of FRP, the most advanced composite material (generally Advanced
(called Composite), products are made using a combination of long fibers and B-stage thermosetting resin. When making FRP products using thermoplastic resin, short fibers are generally used as reinforcing fibers. However, when short fibers are used as reinforcing fibers, there are limitations in terms of physical properties.Furthermore, the short fibers are exposed on the product surface and become rough, resulting in an inferior appearance. When a synthetic resin is used, there are problems such as large changes over time, problems with processability including storage, and the need for curing (hardening by heat treatment) as a process. Therefore, recently,
Composite materials that combine long fibers and thermoplastic resins have begun to be considered. However, such composite materials have a problem in that they are difficult to handle because they are hard. As a solution to this problem, it has been considered to make a woven fabric from fibers made of the same resin as the thermoplastic resin that is to be melted and turned into a matrix resin, and to combine it with the thermoplastic resin to form a composite material. Also,
Another method has been considered in which a reinforcing fiber fabric and a matrix resin film are made separately, and then they are alternately laminated during molding and the films are melted. When composite materials made by these methods are laminated and molded, the fabric generally lacks elasticity and the shape of the molded product is restricted, making it difficult to mold into curved surfaces, especially spherical surfaces, and the adhesion of fibers is not always good. The problem is that there is no. Also, an important fact is that when a composite material reinforced with long fiber fabric is molded to have a curved surface, the long fiber fabric breaks during molding, resulting in the same reinforcement as when short fibers are used as reinforcing fibers. It is often only effective, and in some cases,
The composite material itself may also tear. Also,
Even if long fibers are used for reinforcement in a unidirectional arrangement, if they are molded without applying sufficient tension to the fibers, the tensile fibers and elastic modulus may not increase as expected or may easily vary, making it unsatisfactory. I can't get any results. Further, U.S. Patent No. 3,664,909, U.S. Pat. No. 3,713,962, and U.S. Pat. No. 3,850,723 disclose a composite mat structure for compression molding in which fiber strand mat is impregnated with resin, and a method for manufacturing the same. As described above, this composite material is easier to form into a curved surface, especially a spherical surface, than the reinforcing fabric described above, but its mechanical properties are inferior and the surface tends to be rough. (Problems to be Solved by the Invention) The present invention solves the problems of the prior art as described above, and can be molded into a curved surface without reducing strength or damaging the product, and also improves the smoothness of the product surface. The object of the present invention is to provide a composite material having excellent appearance and sufficient strength, and a method for producing the same. (Means for Solving the Problem) As a result of intensive studies to achieve the above object, the present inventors found that it is sufficient to laminate a long fiber layer aligned in a certain direction and a stretchable film. This discovery led to the present invention. That is, the present invention provides a composite material comprising a laminate in which long fiber layers aligned in a certain direction and a stretchable film are laminated, and at least a portion of the laminate forms a curved surface. A method for manufacturing a composite, which comprises aligning the body and tension fibers in a certain direction, laminating them on a stretchable film, forming a laminate, and then shaping the laminate so that at least a portion of the laminate forms a curved surface. It is. The long fibers used in the present invention may be relatively heat-resistant fibers, such as carbon fibers, SiC fibers, glass fibers, aramid fibers, aromatic polyetheramide fibers, arylate fibers, polyester fibers, polyamide fibers, etc. Depending on the thermoplastic polymer used to form the film, polyolefin fibers may be used, or natural fibers such as hemp may be used depending on the case. However, fibers with high strength and elastic modulus are preferred. On the other hand, the stretchable film used in the present invention can be made of any resin, and there is no particular limitation on the material as long as it serves as a matrix resin for a composite material and can be made into a film. For example, thermoplastic resins such as polyamide (nylon, etc.), polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polycarbonate, polyvinyl compound (polystyrene), polyvinyl chloride, polyacrylonitrile, polyether, polysulfon, etc. can be mentioned. In general, it is preferable that the material is heat resistant and amorphous, or even crystalline but shows little change over time, but it is more preferable that the material has a low melt viscosity. Therefore, optically anisotropic polymers are also used. Furthermore, films made of thermosetting resins such as epoxy resins, acrylic acid resins, and unsaturated polyester resins can also be used. Furthermore, a thermoplastic resin film and a thermosetting resin film may be used together. For example, a thermosetting resin film may be laminated on a thermoplastic resin film, and long fibers may be laminated thereon;
Long fibers may be laminated on a thermoplastic resin film, and a thermosetting resin film may be laminated thereon. These resins have excellent extensibility when made into a film, and when molded with a matrix resin, it is desirable to have good adhesion and compatibility between the resins, so elastic polymers etc. It is also effective to mix and modify with polymer blends, molecular composites, etc. For the purpose of adhesion to fibers, improvement of resin properties after molding, etc., a thermosetting resin or the like can be added to bridge the polymer. The fiber and film combination may optionally be of the same polymer. For example, polymetaphenylene isophthalamide fibers and films can be combined. The composite of the present invention consists of a laminate in which the long fibers are aligned in a certain direction and laminated on the stretchable film. FIGS. 1 and 2 are longitudinal cross-sectional views showing examples of the laminate used in the present invention,
In FIG. 1, a layer of long fibers 2 aligned in a uniform manner is adhered to a stretchable film 1 by means of an adhesive 3. Further, in FIG. 2, a long fiber layer 2 aligned in a certain manner is fused to an extensible film 1. It is also possible to further add a resin layer to this laminate. For example, a film made of thermoplastic resin may be adhered onto the long fiber layer 2, or a solution or melt of the thermoplastic resin may be applied onto the long fiber layer 2. When the resin layer is added in the form of a film, it is preferable that the film and the stretchable film 1 have different strengths and elastic moduli, since this facilitates handling during processing. Heat-fusible binder fibers can also be added to the long fiber layer 2. In order to laminate the long fiber layer 2 onto the stretchable film 1, for example, the stretchable film is continuously fed out from the film forming device, while the long fibers are opened,
The two may be stacked by supplying them while aligning them. At this time, it is preferable to restrain the long fibers with other elastic fibers to such an extent that they can be stretched in a direction perpendicular to the fiber axis, for ease of handling. When sending out the film, it is also possible to make the film in advance from thermoplastic resin and then pay it out. however,
In this case, it is preferable that the film has not been used for a long time after being formed, and it is also preferable to preheat it. Thermoplastic resins generally crystallize after molding, and crystallization progresses over time, but in the case of the present invention, it is preferable that crystallization of the film does not progress. When flexibility is required for the composite material, it is preferable that the film be thin, and therefore stretching may be performed after film formation, but care must be taken to prevent excessive crystallization and orientation. FIG. 3 is a schematic view showing an example of an apparatus for manufacturing a laminate of a long fiber layer and a film in which a film is further added on top of the long fiber layer. After the films 1 and 1' extruded from the two film forming machines 11 and 12 are cooled and solidified by cooling drums 13 and 13' and cooling rollers 14 and 14', they are transferred to the pulling machine 1.
Overlap with 5. In this case, one film 1' is expected on the heated drum 16. It may be better to preheat the film depending on the type of thermoplastic resin and film forming method. Also, when using two films, melt only one film,
It is preferable to just fuse the other one in its original form, and therefore it is preferable to increase the crystallization and orientation of one of them than the other, or to adjust the preheating before hot pressing. FIG. 3 shows an example of a method for performing such an operation in which one of the films is preheated. On the other hand, the reinforcing long fibers 2 unwound from the package 17 are opened by a fiber opening machine 18 and aligned by a screen 19, and then an adhesive such as resin or the same resin as the films 1, 1' is applied in a dipping tank 20. and preheater 21
The film is preheated with a temperature control device, and then inserted between films 1 and 1' using a pulling machine 15. Treatment of the reinforcing long fibers 2 with an adhesive or resin and preheating with the preheater 21 have the effect of increasing adhesiveness to the films 1 and 1'. The films 1, 1' and the reinforcing long fibers 2, which are superimposed on each other by a pulling machine 15, are preheated by a preheating drum 22. Preferably, the preheating is performed from substantially both sides of the laminated sheet. As mentioned above, when a thermoplastic resin film and a thermosetting resin film are combined, it is desirable that the preheating temperatures for both sides be different. Next, this sheet is pressed at high temperature and pressure using a hot press machine 23 such as a calender roll to form a laminate. This heat pressure machine 2
Conditions 3 are appropriately selected depending on the thermoplastic resin used. The thus obtained laminate is wound up by a winding machine 24. The thus obtained laminate may be used as it is, or a plurality of such laminates may be further laminated and formed into a composite body having at least a partially curved surface, particularly a spherical surface, by thermocompression bonding, adhesion, fusing, or melting by press molding or the like. . When the laminate consisting of the reinforcing long fibers and the film is further laminated and molded, it is preferable to sandwich an adhesive, an adhesive film, etc. depending on the type of film or fiber. Moreover, a cosmetic film can also be used as the outermost layer. The cosmetic film preferably has a high surface hardness. FIG. 4 shows an example in which a plurality of laminates are laminated on a stretchable film 1, in which long fiber layers 2 aligned in a certain direction are adhered by an adhesive 3. In this case, the long fibers of each laminate are arranged in substantially the same direction. Furthermore, it is preferable to laminate a plurality of laminates so that the long fiber arrangement directions of each laminate form an angle with respect to each other, since a molded product having uniform strength in any direction can be obtained. Figures 5 and 6 show a plurality of laminates in which a stretchable film 1 and long fiber layers 2 aligned in a certain direction are laminated, and the arrangement of the long fibers 2 in each laminate. It shows an example where the directions are at an angle to each other. In addition, 4 is an adhesive film, 5
is a cosmetic film. In order to form a curved surface on at least a portion of the laminate, the laminate may be placed in a mold having a curved surface and heated and pressed. The laminate used in the present invention is composed of long fiber layers aligned in a certain direction and a stretchable film, so when it is formed into a curved surface by press molding etc. As a result, the distance between long fibers increases, and the film stretches. Therefore, the reinforcing long fibers will not be cut during molding and the strength of the composite will not decrease, and the composite itself will not be torn. Furthermore, since the long fibers aligned in one direction are laminated and fixed on a stretchable film, even if sufficient tension is not applied to the long fibers during molding, the tensile strength and elastic modulus may not increase or variations may occur. I never get stuck. In addition, since long fibers are used as reinforcing fibers, a more sufficient reinforcing effect can be obtained than when short fibers are used. There is no such thing as becoming. (Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Polyethylene terephthalate with η=0.79, which was polycondensed from dimethyl terephthalate and ethylene glycol, was extruded from an extruder at 290°C to obtain a film (unstretched film) with a thickness of 0.05 mm. On the other hand, a solution of polyethylene terephthalate dissolved in orthochlorophenol was applied to carbon fiber made from polyacrylonitrile (trade name: Torayca T-300, manufactured by Toray Industries, Inc.). The fibers were placed in a semi-dry state on the polyethylene terephthalate film in one direction. The specimen was sandwiched between plates to dry. In this way, a thin sheet material was obtained in which carbon fibers were aligned in one direction and adhered to a polyester film. Eight sheets of this thin sheet were stacked one on top of the other so that the carbon fiber arrangement directions of each thin sheet made an angle of 45° with respect to each other, and the sheets were placed in a partially spherical mold with a radius of 200 mm and pressed. The mold was preheated to approximately 150°C. Also,
The stacked thin sheets were pressed at a temperature of 300°C and a compression load of 5 tons. After reaching 300℃, hold at that temperature for 3 minutes, then cool the mold by placing it in water containing ice.
A sample piece with a thickness of 1 mm was obtained. The density of this molded product is approximately
The fiber volume fraction (Vf) was approximately 30%, the tensile strength in ^the fiber axis direction was 58 Kg/mm ² , and the tensile modulus was 3500 Kg/mm ² . Moreover, the surface of the molded product was smooth and had a good appearance. Example 2 Glass fibers (10μ diameter) were coated with Aron Alpha (adhesive manufactured by Toagosei Co., Ltd.), and when semi-dry, they were aligned in a certain direction on a polypropylene film (20μ) and adhered tightly, and used as a composite material precursor. of thin leaves were obtained. The obtained thin material was pressed as it was using the mold with the spherical surface used in Example 1, and it was confirmed that the fibers spread almost symmetrically. Furthermore, five sheets of the obtained thin leaf material were stacked and molded using the same mold with a spherical surface used in Example 1. The mold was preheated (estimated temperature: 70°C) and heated to 180°C after the thin material was installed. After cooling, a molded product with a partially spherical surface was obtained. Example 3 A polymer of polymetaphenylene isophthalamide (η=1.3) was dissolved in N-methyl-2-pyrrolidone with calcium chloride to form a 40% solution. This was extruded into a N-methyl-2-pyrrolidone aqueous solution to form a film, stretched and washed with water to form a film (10μ). On the other hand, the aromatic polyamide fiber Technora (manufactured by Teijin Ltd., tensile elongation at break of about 2%) (6μ diameter) was pulled in one direction and a solution of polymetaphenylene isophthalamide in N-methyl-2-pyrrolidone was added to it. When the film was semi-dry, the above-mentioned polymetaphenylene isophthalamide film was pressed to obtain a thin film. Eight sheets of this thin sheet were stacked one on top of the other so that the fiber arrangement directions of the thin sheet sequentially formed an angle of 90° to each other, and the mold was molded using the mold provided with the partially spherical surface of Example 1. The mold was heated to 360°C in advance, the press temperature was 360°C, and the press load was 10 tons. The obtained molded product is
It had a density of 1.35 g/cm ³ , a volume fiber ratio of about 20%, a tensile strength in the fiber direction of 26 Kg/mm ² , and a tensile modulus of 760 Kg/mm ² . Moreover, the surface of the molded product was smooth and had a good appearance. Example 4 Bisphenol A polycarbonate was dissolved in methylene chloride, applied to carbon fibers, and dried to obtain core-sheath fibers. The obtained core-sheath fibers were heated, aligned in one direction, and pressed onto a polycarbonate film. After cooling, the aforementioned methylene chloride solution of polycarbonate was applied to the fiber side and dried. Eight of the obtained thin sheets were stacked one on top of the other so that the fiber arrangement directions of each thin sheet made an angle of 90° with respect to each other, and molded using the spherical mold of Example 1. The tensile strength of this molded product is 54Kg/mm ² and the tensile modulus is 1120.
It was Kg/ ^mm2 . Moreover, the surface of the molded product was smooth and had a good appearance. Example 5 A small amount (about 0.3%) of water was added to ε-caprolactam, the atmosphere was replaced with nitrogen, and the temperature was maintained at 250°C to obtain a polymer. After thoroughly washing this polymer with water and drying it,
A film (20μ) was obtained by extrusion at 270°C using an extruder. Commercially available Technora fibers were soaked in a solution of polymetaphenylene isophthalamide in N-methyl-2-pyrrolidone, pulled up, loosened, and dried. When semi-dried, these fibers were arranged in one direction on a commercially available unstretched nylon 6 film at 180°C and 250°C.
Samples were obtained by hot pressing at Kg/ ^mm2 . This sample could be molded using the partially spherical mold used in Example 1, and had a smooth surface and good appearance. Example 6 A fiber and film composite was made by a method that included an adhesive layer. Commercially available carbon fiber (manufactured by Toray Industries, Inc.: T-400 carbon fiber)
and polyethylene terephthalate composite material samples were made. That is, polyethylene terephthalate produced by a transesterification method was made into a film with a thickness of 50 μm by a melt extrusion method. No special stretching was performed. The above carbon fibers are opened and aligned in one direction,
It was wrapped around a metal frame, attached with polyethylene terephthalate film, and pressed at 180°C. This carbon fiber/polyethylene terephthalate film adhesive has a polyethylene terephthalate content of 68g/m ² ,
The carbon fiber content was 36g/ ^m2 . This reinforcing fiber-film adhesive is stacked in 10 layers so that the fiber arrangement direction of each adhesive makes an angle of 90° with respect to each other, and a 50 μm polyethylene terephthalate film is stacked on both outer sides, and between each of these sheets. A polyethylene film thermosetting hot melt adhesive was sandwiched between the two, and the whole was placed in the mold used in Example 1.
Pressed at 150°C and 100Kg/cm ² . The direction of the carbon fibers in each layer was the same. The data of the obtained molded product having a spherical surface were as follows. Density 1.45 g/cm ³ Average volume fiber ratio 20.5% Average tensile strength 37.6 Kg/mm ² Average tensile modulus 690 Kg/mm ² The molded product had a smooth surface and good appearance. Example 7 A laminate was produced using the apparatus shown in FIG. Polyethylene terephthalate was formed into a film (approximately 5μ thick) using film forming apparatuses No. 11 and 12. The η of the polymer used was 0.65, and the temperature of the extruder in the apparatus was 300°C. Carbon fibers with a diameter of about 10 μm were used as the long fibers. Commercially available tensile strength 300Kg/mm ² , tensile modulus 25000
Kg/mm ² carbon fiber. The fibers were spread using a tow spreader used to produce long fiber nonwoven fabrics, drawn and preheated using a heating roller. The temperature of the opened tow was measured by sliding the sensor part of a surface thermometer and was 150°C. The carbon fibers are sandwiched between the films sent from the film forming apparatuses 11 and 12 above, aligned, and then heated using a roller preheater.
The temperature was raised to 150℃. Next, this was processed using a hot pressure roller at a roller linear pressure of 50 Kg/cm and a temperature of 200° C. to obtain a laminate. After cooling, the obtained laminate has a volumetric fiber ratio (Vf)
51%, tensile strength 151Kg/mm ² , tensile modulus 13000Kg/
It was warm in ^mm2 . This laminate is made so that the fibers are aligned in the same direction as each other.
Stack 8 sheets at a 90° angle and place them in the mold used in Example 1, 100Kg/mm ² , 280℃
The composite material was molded into a spherical composite material by hot pressing. The resulting molded product had a tensile strength of 70 Kg/mm ² and a tensile modulus of 675 Kg/mm ² . Moreover, the surface of the molded product was smooth and the appearance was good. Example 8 A laminate of polyethylene terephthalate resin was obtained in the same manner as in Example 7. However, the extruder No. 11 was not used, and the film layer was a single layer laminate with respect to the long fiber layer. This laminate was used in Example 7 when molding a curved surface.
It was easier to handle than the laminate. The physical properties of the obtained molded product were almost the same as those of Example 7, and the appearance was also good. Example 9 A polybutylene terephthalate resin laminate was obtained in the same manner as in Example 7. Polybutylene terephthalate was formed into a film using film forming apparatus Nos. 11 and 12. The η of the polymer used is
0.72, and the temperature of the extruder in the film forming apparatus was 290°C. Carbon fiber was used as the long fiber. It is a commercially available carbon fiber with a tensile strength of 300 Kg/mm ² and a tensile modulus of 25000 Kg/mm ² . The fibers were opened using a tow opening machine used for producing long-fiber nonwoven fabrics, drawn in alignment, and heated with a heating roller. The temperature of the opened tow was measured by sliding the sensor part of a surface thermometer and was 150°C. Sandwich the carbon fibers between the obtained films, align them,
The temperature was raised to 180°C using a roller preheater, and a laminate was obtained by processing with a hot pressure roller at a linear pressure of 50 kg/cm and a temperature of 200°C. After cooling, the obtained laminate has a volumetric fiber ratio (Vf)
50%, tensile strength 145Kg/mm ² , tensile modulus 11000Kg/
It was warm in ^mm2 . This laminate is made so that the fibers are aligned in the same direction as each other.
Eight sheets were stacked at an angle of 90°, placed in the mold used in Example 1, and hot-pressed at 100 kg/mm ² and 280° C. to form a composite material molded product having a spherical surface. The resulting molded product had a tensile strength of 72 Kg/mm ² and a tensile modulus of 600 Kg/mm ² . Moreover, the surface of the molded product was smooth and the appearance was good. Example 10 A laminate was produced by modifying the apparatus shown in FIG. The devices Nos. 11 and 12 were used to extrude a polymer solution from a die into a coagulation bath to form a film.
Polymetaphenylene isophthalamide (η=
1.28) with calcium chloride and N-methyl-2-
It was dissolved in pyrrolidone to make a 42% solution. This solution was extruded into a coagulation bath consisting of an aqueous solution of N-methyl-2-pyrrolidone and calcium chloride, washed with water to remove calcium chloride, and then dried. Polymetaphenylene isophthalamide fibers (trademark: Konex) were opened using the same opening machine as in Example 7 and aligned. This film and fibers were laminated and heated using a preheater (heating drum). The temperature of the drum was 280°C. This laminate was subsequently hot pressed. The temperature of the thermopressure calendar was 320°C and the pressure was 100Kg/cm ² . The obtained laminate was cut and eight more sheets were combined.
Placed in the mold used in Example 1, 100Kg/cm ² , 360℃
It was heated and pressed. The surface of the obtained molded product was smooth and had a good appearance. Example 11 In FIG. 3, a polyethylene terephthalate film was produced using only a film forming apparatus. The η of the polymer is 0.64. After opening the carbon fibers, they were passed through a solution of polyethylene terephthalate dissolved in orthochlorophenol. When the obtained carbon fibers were dried and the amount of resin was measured, it was found to be 24% based on the carbon fibers. The resin-coated carbon fibers were heated to 180°C, overlapped with a film, further heated to 200°C, and hot-pressed using a calendar roll at a linear pressure of 100 kg/cm and a temperature of 240°C. The obtained laminate has a volume fiber ratio of 49% and a tensile strength of
The tensile modulus was 138Kg/mm ² and the tensile modulus was 1280Kg/mm ² . Example 1: Eight sheets of this laminate were stacked so that the fiber arrangement directions made an angle of 45° to each other.
It was placed in the mold used in 2003 and hot-pressed at 100 kg/cm ² at 290°C to form a composite material molded product with a spherical surface. The resulting molded product had a tensile strength of 74 Kg/mm ² and a tensile modulus of 650 Kg/mm 2 .
It was warm in ^mm2 . Moreover, the surface of the molded product was smooth and had a good appearance. Example 12 Commercially available carbon fiber (T-300 carbon fiber manufactured by Toray Industries, Inc.)
and polyetheretherketone composite samples were made. That is, commercially available polyetheretherketone (hereinafter abbreviated as PEEK) was melt-extruded to a thickness of approximately
It was made into a 50μ film. No special stretching was performed. After opening the above carbon fiber and wrapping it around a metal frame, it is layered on a PEEK film,
Pressed at ℃. This carbon fiber/PEEK film adhesive had a PEEK content of 95 g/m ² and a carbon fiber content of 5 g/m ² . The resulting carbon fiber bonded PEEK film
Cut into squares of 250mm x 250mm and arrange them one after another so that the reinforcing fibers of each adhesive are arranged at a 90° angle to each other.
Twelve layers were stacked and hot pressed at 280°C and 100Kg/cm ² . The results of measurement of the obtained reinforcing plate were as follows. Average tensile strength: 25Kg/mm ² Tensile modulus at break: 680Kg/mm ^2Similarly , this composite intermediate material was stored in a hot air dryer at 290℃ for 30 minutes, and then removed and immediately heated to 250℃.
It was press-molded in a tray-shaped mold kept at ℃, and the mold was placed in cold water to cool and taken out.
The measurement results of the physical properties of the obtained molded product showed the following values, which are almost the same as those of the composite material plate used as the intermediate material. Tensile strength: 18.2 Kg/mm ² Tensile modulus: 528 Kg/mm ² The molding made only of PEEK without adding fibers and with other conditions as in the example was as follows. Tensile strength 6.2Kg/mm ^2Tensile modulus 203Kg/ ^mm 2Example 13

[Formula] and

Optically anisotropic polyester consisting of [formula] is melted and extruded to a thickness of
It was made into a 200μ film. On the other hand, carbon fiber T-300 was aligned and wound around a metal frame, and then superimposed on the polyester film and bonded by pressing at 280° C. and 50 kg/cm ² .
At this time, the extrusion direction during film molding and the direction of the fibers were the same. Twelve layers of this thin sheet material were stacked so that the fibers were arranged in alternating directions at right angles, heated in a dryer at 290°C, and pressed at 300°C to form a curved surface. The physical properties of the obtained molded product were as follows. Tensile strength: 20.1 Kg/mm ² Tensile modulus: 399 Kg/mm ² The following moldings were made using only the polyester without adding fibers and with other conditions as in the example. Tensile strength: 17.5 Kg/mm ² Tensile modulus: 225 Kg/mm ² Example 14 The optically anisotropic polyester used in Example 13 was made into a 60 μm thick film by melting and extrusion. On the other hand, carbon fiber T-300 was aligned and wound around a metal frame, and then superimposed on the polyester film and bonded by pressing at 280° C. and 50 kg/cm ² .
At this time, the extrusion direction during film molding and the direction of the fibers were the same. Twelve layers of this thin sheet material were stacked so that the fibers were arranged in alternating directions at right angles, heated in a dryer at 290°C, and pressed at 300°C to form a curved surface. The physical properties of the obtained molded product were as follows. Tensile strength: 53.5 Kg/mm ² Tensile modulus: 1304 Kg/mm ² The following moldings were made only of the polyester without adding fibers and with other conditions as in the example. Tensile strength: 20.9 Kg/mm ² Tensile modulus: 700 Kg/mm ² (Effects of the invention) According to the present invention, a laminate made of reinforcing fibers and a film can be formed into a curved surface without a decrease in strength or damage. It is possible to provide a curved composite with excellent surface smoothness and appearance and sufficient strength. The composite of the present invention can be effectively used, particularly as bodies for various vehicles such as automobiles, various containers, chairs, benches, and the like.

[Brief explanation of the drawing]

1 and 2 are longitudinal cross-sectional views showing an example of a laminate used in the present invention, FIG. 3 is a schematic diagram showing an example of an apparatus for carrying out the method of the present invention, and FIG. 4 is a longitudinal sectional view showing an example of a laminate used in the present invention. A vertical cross-sectional view showing an example in which the laminate is further laminated into a plurality of layers, and FIGS. 5 and 6 are perspective views showing other examples in which the laminate is further laminated in a plurality of layers. 1...Stretchable film, 2...Long fiber layer,
3... Adhesive, 11, 12... Film forming machine, 15...
Pulling machine, 18... Spreading machine, 19... Screen,
23...Heat pressure machine.

Claims (1)

[Claims] 1. Consisting of a laminate in which long fiber layers aligned in a certain direction and a stretchable film are laminated, at least a part of the laminate forms a curved surface. complex. 2. The composite according to claim 1, wherein a resin layer is formed on the long fiber layer side of the laminate. 3. The composite according to claim 2, wherein the resin layer is a stretchable film. 4. The composite according to claim 1, wherein a plurality of the laminates are further laminated. 5 The alignment direction of the long fibers in each laminate is
5. A composite body according to claim 4, which is angled with respect to one another. 6. A method for producing a composite, which comprises aligning long fibers in a certain direction, laminating them on a stretchable film to form a laminate, and then shaping the laminate so that at least a portion of the laminate forms a curved surface. . 7. The method for manufacturing a composite according to claim 6, wherein opened and aligned long fibers are laminated on a stretchable film sent out from a film forming device. 8. The method for producing a composite according to claim 6, wherein long fibers aligned in a certain direction are laminated between two stretchable films. 9. The method for manufacturing a composite according to claim 8, wherein opened and aligned long fibers are laminated between stretchable films sent out from two film forming apparatuses. 10. The method for producing a composite according to any one of claims 6 to 9, which comprises fixing long fibers to a film. 11. The method for manufacturing a composite according to any one of claims 6 to 10, which further comprises laminating a plurality of laminates. 12. The method for manufacturing a composite according to claim 11, wherein the laminated bodies are laminated so that the alignment directions of the long fibers in each laminate form an angle with each other.