JPWO2013187220A1 - Carbon fiber composite material, molded product using the same, and production method thereof - Google Patents

Abstract

A pellet having a core-sheath structure in which the core component is made of carbon fiber and the sheath component is made of the first thermoplastic resin and the second thermoplastic resin are melted, and the molten pellet and the second thermoplastic resin are melted at a predetermined temperature. A method for producing a carbon fiber composite material that is kneaded by using a method. Moreover, the manufacturing method of the molded article which melts and shape | molds the carbon fiber composite material manufactured using such a manufacturing method. Furthermore, an island phase composed of the first thermoplastic resin is dispersed in the sea phase composed of the first thermoplastic resin, the second thermoplastic resin, and the carbon fiber, and composed of the second thermoplastic resin. A carbon fiber composite material characterized by having the structure described above, and a molded product formed by molding the carbon fiber composite material. According to these, improvement in physical strength is realized, post-processing is easy, carbon fiber composite materials optimized for the production of high-rigidity molded products, molded products formed by molding them, and production thereof A method can be provided.

Description

  The present invention relates to a carbon fiber composite material that is improved in mechanical properties and easy to post-process and is suitable for extrusion molding, a molded product using the carbon fiber composite material, and the carbon fiber composite material and the molded product. It relates to a manufacturing method.

  In the prior art, a carbon fiber composite material has been obtained by preparing a prepreg in which carbon fiber is impregnated with a liquid thermosetting resin and subjecting it to autoclaving at high temperature and high pressure. However, expensive equipment such as low-temperature equipment for storing prepregs at low temperatures and high-temperature equipment for autoclaves is required, and it has been a heavy burden to have these equipments.

Therefore, as a method of using a thermoplastic resin that is easy to handle instead of a conventional thermosetting resin, Patent Document 1 discloses a molding material in which a thermoplastic resin is coated around a continuous carbon fiber bundle. Is cut to 50 mm or less. In such a configuration, it is preferable to use a low-viscosity thermoplastic resin in order to improve the adhesion between the carbon fiber and the resin.
However, the low-viscosity resin is suitable for injection molding in which molding is performed by filling the resin in the mold, but in extrusion molding in which the molten resin is poured from the extruder into a die, the molded product However, the shape is not stable, and the machinability and mechanical properties tend to be insufficient, and a method of using a high-viscosity thermoplastic resin together has been sought.

Thus, as a method of using a high viscosity thermoplastic resin, Patent Document 2 discloses a method for producing a pellet in which a bundle of carbon fibers is coated with a low viscosity thermoplastic resin and then coated with a high viscosity thermoplastic resin. It is disclosed.
However, when the pellets obtained by this method are used for extrusion molding, the low-viscosity thermoplastic resin and the high-viscosity thermoplastic resin are completely separated, and the dispersion of carbon fibers in the resin becomes insufficient. In many cases, cracks and voids are generated at the time of molding or after molding, and it was difficult to use them as products.

Therefore, Patent Document 3 discloses a long fiber reinforced synthetic resin strand formed by impregnating synthetic resin into a long fiber that has been aligned, or a long fiber reinforced synthetic resin pellet cut to an arbitrary length, and having a fiber content of What is comprised by the high layer and the layer with a low fiber content rate is disclosed. And, as an effect of the invention obtained by such a strand or pellet, the impact strength of the molded product is good because the strand or pellet maintains a state in which the long fibers are bundled and aligned, the fiber The resin for impregnating the bundle has a low viscosity and the impregnation speed is fast. It is mentioned that since it is a pellet, a molded product having high strength and high elasticity can be obtained.
However, when such strands or pellets are used for extrusion molding, since the long fibers are bundled and converged, the carbon fibers cannot be defibrated in the molten resin, and are complicated. When formed into a different shape, the carbon fibers are in a dense state. As a result, not only does the spring back cause the resin to be ejected by the long fibers during extrusion molding, it becomes difficult to obtain the desired shape, but the carbon fibers are not evenly dispersed throughout the resin, but instead of the molded product. May cause cracks and voids.

Japanese Utility Model Publication No. 60-62912 JP 2009-263482 A JP-A-6-320536

  The present invention has been made in view of the problems of the prior art, and the object thereof is a carbon fiber composite material comprising a thermoplastic resin and carbon fibers, excellent in mechanical properties and processability, and suitable for extrusion molding. An object of the present invention is to provide a molded article using the fiber composite material, and a method for producing the carbon fiber composite material and the molded article.

  In order to solve the above-described problems, a carbon fiber composite material according to the present invention, a molded product using the carbon fiber composite material, and a manufacturing method thereof have the following configurations.

(1) A pellet having a core-sheath structure in which the core component is made of carbon fiber and the sheath component is made of the first thermoplastic resin and the second thermoplastic resin are melted, and the molten pellet and the second thermoplastic resin are melted. In the method for producing a carbon fiber composite material, wherein the second thermoplastic resin has a higher viscosity than the first thermoplastic resin at the predetermined temperature. Method.
(2) The method for producing a carbon fiber composite material according to (1), wherein the viscosity of the second thermoplastic resin is 10 to 750 times the viscosity of the first thermoplastic resin at a predetermined temperature.
(3) The viscosity of the first thermoplastic resin at a predetermined temperature is 50 to 500 poise, and the viscosity of the second thermoplastic resin at a predetermined temperature is 1,000 to 10,000 poise (1) or (2) Of carbon fiber composite material.
(4) Any of (1) to (3), wherein the predetermined temperature is higher than the melting point of the second thermoplastic resin, and the difference between the predetermined temperature and the melting point of the second thermoplastic resin is 30 to 90 ° C. Of carbon fiber composite material.
(5) The manufacturing method of the carbon fiber composite material in any one of (1)-(4) whose melting | fusing point of a 2nd thermoplastic resin is 100-370 degreeC.
(6) The method for producing a carbon fiber composite material according to any one of (1) to (5), wherein carbon fibers are further added to the melted pellets and the second thermoplastic resin.
(7) The method for producing a carbon fiber composite material according to any one of (1) to (6), wherein the carbon fiber composite material contains carbon fiber in a proportion of 5 to 60% by weight.
(8) A method for producing a molded product, comprising melting a carbon fiber composite material produced by the method for producing a carbon fiber composite material according to any one of (1) to (7), and thereafter molding the material.
(9) The method for producing a molded article according to (8), wherein the carbon fiber composite material is molded by a melt extrusion method or a solidification extrusion method.
(10) After forming a carbon fiber composite material to form an intermediate molded body, the intermediate molded body is further molded by a press molding method, a vacuum molding method, a blow molding method, or a bending process. Production method.
(11) The method for producing a molded article according to (10), wherein the intermediate molded body is hot pressed under conditions of a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 ° C.
(12) The method for producing a molded article according to (10), wherein the intermediate molded body is vacuum-molded under conditions of a pressure of 1 × 10 ^{−5 to} 0.05 MPa and a temperature of 100 to 370 ° C.
(13) The method for producing a molded article according to (10), wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.
(14) The method for producing a molded article according to any one of (10) to (13), wherein the intermediate molded body is molded in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric, or a carbon fiber composite material. .
(15) An island phase composed of the first thermoplastic resin is formed in the sea phase composed of the first thermoplastic resin, the second thermoplastic resin and the carbon fiber, and composed of the second thermoplastic resin. A carbon fiber composite material having a dispersed structure.
(16) The carbon fiber composite material according to (15), wherein the refractive index of the first thermoplastic resin is different from the refractive index of the second thermoplastic resin.
(17) The carbon fiber composite material according to (15) or (16), wherein 50% by weight or more of the carbon fibers contained in the carbon fiber composite material is present in the island phase.
(18) The carbon fiber composite material according to any one of (15) to (17), comprising carbon fiber at a ratio of 5 to 60% by weight.
(19) The carbon fiber composite material according to any one of (15) to (18), wherein an average diameter of the island phase is 10 nm to 100 μm.
(20) The carbon fiber composite material according to (19), wherein the average diameter of the island phase is 10 nm to 1 μm.
(21) A molded product formed by molding the carbon fiber composite material according to any one of (15) to (20).
(22) The molded article according to (21), which is molded by a melt extrusion method or a solidification extrusion method.
(23) The molding according to (21), wherein after forming a carbon fiber composite material to form an intermediate molded body, the intermediate molded body is further molded by a press molding method, a vacuum molding method, a blow molding method or a bending process. Goods.
(24) The molded article according to (23), wherein the intermediate molded body is hot-pressed under conditions of a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 ° C.
(25) The molded article according to (23), wherein the intermediate molded body is vacuum-molded under conditions of a pressure of 1 × 10 ^{−5 to} 0.05 MPa and a temperature of 100 to 370 ° C.
(26) The molded article according to (23), wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.
(27) The molded article according to any one of (23) to (26), wherein the intermediate molded body is molded in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric, or a carbon fiber composite material.

By using the carbon fiber composite material of the present invention, cracks and voids generated in the product can be suppressed in extrusion molding. As a result, post-processing such as pressing or bending by cutting or heat treatment can be easily performed.
In addition, since the resin is thermoplastic, it is possible to provide a molded product that can be easily recycled.

It is a schematic perspective view which shows the pellet which consists of a carbon fiber composite material which concerns on one embodiment of this invention. It is a partial expanded sectional view for demonstrating the structure of the pellet shown in FIG. 1, (a) is a schematic cross section which shows an example of the structure of a carbon fiber composite material, (b) is a side cross section of a carbon fiber composite material. It is a cross-sectional observation figure which shows an example of the result observed with the electron microscope. It is a schematic perspective view which shows an example of the pellet which has the conventional 3 layer structure. It is a schematic perspective view which shows an example of the pellet which has the conventional 2 layer structure. It is a manufacturing process figure which shows an example of the manufacturing method of the pellet of FIG. It is a manufacturing-process figure which shows the other example of the manufacturing method of the pellet of FIG. It is a manufacturing process figure which shows an example of the manufacturing method of the pellet of FIG. It is a schematic longitudinal cross-sectional view which shows an example of the die | dye used for manufacture of the pellet of FIG. It is a manufacturing process figure which shows an example of the manufacturing method of the sheet | seat by a melt extrusion method. It is a manufacturing process figure which shows an example of the manufacturing method of the pipe by a melt extrusion method. It is a schematic sectional drawing which illustrates the cross-sectional shape of the pipe manufactured by the manufacturing method of FIG. It is a manufacturing process figure which shows an example of the manufacturing method of the round bar by a melt extrusion method. It is a schematic sectional drawing which illustrates the cross-sectional shape of the round bar manufactured by the manufacturing method of FIG. It is a manufacturing process figure which shows an example of the manufacturing method of the irregular shape goods by a melt extrusion method. FIG. 15 is a schematic cross-sectional view illustrating a cross-sectional shape of a deformed product manufactured by the manufacturing method of FIG. 14, where (a) illustrates a cross-sectional shape of an I-shaped product, (b) illustrates a cross-sectional shape of an H-shaped product, ( c) shows the cross-sectional shape of the T-shaped variant. It is a manufacturing process figure which shows an example of the manufacturing method of the molded article by the solidification extrusion method. It is a schematic sectional drawing which illustrates the cross-sectional shape of the molded article manufactured by the manufacturing method of FIG. 16, (a) has shown the cross-sectional shape of the extrusion block, (b) has shown the cross-sectional shape of the round bar. It is a flowchart which shows the 1st example of the shaping | molding process by hot press molding, (a) is the process of preparing the carbon fiber composite material sheet as a material, (b) is the process of laminating | stacking a sheet | seat in a metal mold | die, ( c) is a step of putting a laminated body in which sheets are laminated into a predetermined position in the mold, (d) is a step of performing heat press with the mold closed, and (e) is a molded body by opening the mold. (F) shows a step of deburring the molded body to obtain a molded product. It is a flowchart which shows the 2nd example of the shaping | molding process by hot press molding, (a) is the process of preparing the carbon fiber composite material sheet as a material, (b) is the process of putting a sheet | seat in a metal mold | die, (c) Is a step of closing the mold and performing hot pressing, (d) is a step of opening the mold and taking out the molded body, and (e) is a process of deburring the molded body to obtain a molded product. Yes. It is a flowchart which shows the 3rd example of the shaping | molding process by hot press molding, (a) is the process of preparing the carbon fiber composite material sheet as a material, (b) is the process of putting a sheet | seat in a metal mold | die, (c) Is a step of closing the mold and performing hot pressing, (d) is a step of opening the mold and taking out the molded body, and (e) is a process of deburring the molded body to obtain a molded product. Yes. It is a flowchart which shows the 4th example of the shaping | molding process by hot press molding, (a) is the process of heating a carbon fiber composite material sheet, (b) is the process of putting the heated sheet into a metal mold | die, (c). Is a step of closing the mold and performing hot pressing, (d) is a step of opening the mold and taking out the molded body, and (e) is a process of deburring the molded body to obtain a molded product. Yes. It is a flowchart which shows an example of the shaping | molding process by vacuum forming, (a) is the process of heating a carbon fiber composite material sheet, (b) is the process of putting a heated sheet into a metal mold | die, (c) is applying a sheet | seat. (D) shows a step of removing the molded body from the mold, and (e) shows a step of deburring the molded body to obtain a molded product. It is a flowchart which shows an example of the shaping | molding process by blow molding, (a) is the process of heating the sheet | seat holding body which uses a carbon fiber composite material sheet, (b) puts the heated sheet | seat holding body in a metal mold | die. Step (c) is a step of closing the mold and performing blow molding, (d) is a step of opening the mold and taking out the molded product holder, and (e) is a step of removing the holder and deburring the molded body. The step of obtaining a molded product by performing (f) shows a cross-sectional view of the obtained molded product. It is a flowchart which shows the 5th example of the shaping | molding process by hot press molding, (a) is a process which prepares a carbon fiber composite material sheet and glass fiber fabric as a material, (b) is a sheet | seat and fabric in a metal mold | die. A step of laminating, (c) a step of putting a laminate formed by laminating a sheet and a woven fabric into a predetermined position in the mold, (d) a step of closing the die and performing hot pressing, and (e) a step of The step of opening the mold and taking out the molded product, and (f) show the step of deburring the molded product to obtain a molded product. It is a flowchart which shows the 6th example of the shaping | molding process by hot press molding, (a) is a process which prepares a carbon fiber composite material sheet and a thermoplastic resin sheet as a material, (b) is a sheet | seat laminated | stacked in a metal mold | die. (C) is a step of putting a laminated body in which the sheets are laminated into a predetermined position in the mold, (d) is a step of closing the mold and performing hot pressing, and (e) is opening the mold. And (f) shows a step of deburring the molded body to obtain a molded product. It is a flowchart which shows the 7th example of the shaping | molding process by hot press molding, (a) is the process which puts the carbon fiber composite material sheet | seat as a material in a metal mold | die, (b) performs hot press with a metal mold | die closed. Step (c) shows a step of opening the mold and taking out the molded body, and (d) shows a step of deburring the molded body to obtain a molded product. It is a schematic perspective view which shows an example of the secondary process of a molded article, (a) is the profile extrusion product used as the material of secondary processing, (b) is the S-shaped bending product formed by bending the profile extrusion product, (C) has shown the square-shaped bending product formed by bending a profile extrusion product, respectively.

  Hereinafter, the present invention will be described in detail.

  In the method for producing a carbon fiber composite material in the present invention, a pellet having a core-sheath structure in which a core component is made of carbon fiber and a sheath component is made of a first thermoplastic resin and a second thermoplastic resin are melted and melted. In the method for producing a carbon fiber composite material in which the pellets and the second thermoplastic resin are kneaded at a predetermined temperature, the second thermoplastic resin has a higher viscosity than the first thermoplastic resin at the predetermined temperature. It consists of a characteristic method.

  Moreover, this invention also provides the carbon fiber composite material manufactured by the said manufacturing method. That is, the carbon fiber composite material in the present invention is composed of the first thermoplastic resin, the second thermoplastic resin, and the carbon fiber, and the first thermoplastic resin is contained in the sea phase composed of the second thermoplastic resin. It consists of what has the structure where the island phase comprised from resin has disperse | distributed. Such a carbon fiber composite material is sometimes referred to as a hybrid carbon fiber composite resin or a hybrid alloy carbon fiber composite resin. In particular, an island phase having an average diameter (described later) of 1 μm or less has excellent characteristics similar to those of Nanoalloy (registered trademark), and is sometimes called a hybrid nanoalloy carbon fiber composite resin.

  In a carbon fiber composite material used as a molding material, the most important point at the time of molding is high affinity between carbon fiber and resin, that is, high adhesion. Moreover, generally in a thermoplastic resin, adhesiveness with carbon fiber becomes high, so that a viscosity is low. Therefore, for example, it is conceivable to produce a carbon fiber composite material using pellets made of carbon fiber and a low-viscosity resin. However, if only a low-viscosity resin is used as the resin of the carbon fiber composite material, the resin will follow the orientation of the carbon fiber during molding, so that the carbon fiber repels the resin, such as springback, cracks, voids, etc. There is a risk of problems, and it is difficult to obtain the desired molded product. On the other hand, according to the carbon fiber composite material manufactured by the method for manufacturing the carbon fiber composite material, the carbon fiber is encapsulated with the first thermoplastic resin having a relatively low viscosity so that the affinity between the carbon fiber and the resin is increased. By covering the first thermoplastic resin with the second thermoplastic resin having a relatively high viscosity while securing the properties, problems such as springback, cracks and voids can be suppressed, and the target molded product can be obtained. Be able to get. In addition, unlike the carbon fiber composite material in the prior art, since the carbon fiber, the first thermoplastic resin, and the second thermoplastic resin are all uniformly dispersed, a highly rigid molded product can be obtained.

  The refractive index of the first thermoplastic resin is preferably different from the refractive index of the second thermoplastic resin.

  From the viewpoint of securing the affinity between the carbon fiber and the resin, it is preferable that 50% by weight or more of the carbon fibers contained in the carbon fiber composite material exist in the island phase. Further, the ratio of the carbon fibers present in the island phase is more preferably 70% by weight or more, and further preferably 90% by weight or more.

  The fiber diameter of the carbon fiber in the present invention is preferably 0.5 to 20 μm, more preferably 5 to 15 μm. If the fiber diameter is too large, the repulsion will be strong during the heat bending process of the molded product, which may cause twisting and unevenness. Further, if the fiber diameter is thin, the mechanical strength of the molded product may be reduced.

  In the carbon fiber composite material, the proportion of carbon fibers is preferably 5 to 60% by weight, more preferably 15 to 50% by weight, and further preferably 20 to 40% by weight. .

  The predetermined temperature is preferably higher than the melting point of the second thermoplastic resin (or the glass transition point when the second thermoplastic resin is amorphous). The difference between the predetermined temperature and the melting point of the second thermoplastic resin is preferably 30 to 90 ° C, and more preferably 40 to 90 ° C.

  In addition, it is preferable that melting | fusing point of a 1st thermoplastic resin is 100-370 degreeC. Moreover, it is preferable that melting | fusing point of a 2nd thermoplastic resin is 100-370 degreeC.

  The viscosity of the second thermoplastic resin is preferably 10 to 750 times, more preferably 20 to 500 times, more preferably 50 to 200 times the viscosity of the first thermoplastic resin at the predetermined temperature. More preferably.

  Further, at the predetermined temperature, it is preferable that the viscosity of the first thermoplastic resin is 50 to 500 poise, and the viscosity of the second thermoplastic resin is 1,000 to 10,000 poise. Furthermore, at the predetermined temperature, it is more preferable that the viscosity of the first thermoplastic resin is 100 to 300 poise and the viscosity of the second thermoplastic resin is 1,500 poise to 5000 poise.

  The first thermoplastic resin and the second thermoplastic resin may have the same or different resin components. For example, among two types of resins having the same components but different polymerization degrees and viscosities, a resin having a relatively low viscosity is designated as a first thermoplastic resin, and a resin having a relatively high viscosity is designated as a second heat. It can also be used as a plastic resin.

  The thermoplastic resin used to produce the carbon fiber composite material may be a polyolefin (eg, polyethylene, polypropylene (PP), polybutylene, polystyrene) or a polyamide (eg, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, Aromatic nylon) or polyimide, polyamideimide, or polycarbonate, or polyester (eg, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate), or polyphenylene sulfide (PPS), polysulfoxide, or polytetrafluoroethylene , Acrylonitrile butadiene styrene copolymer (ABS), polyacetal, polyether, polyether ether ketone It may be oxymethylene. Moreover, the said thermoplastic resin derivative | guide_body, the copolymer of the said thermoplastic resin, and those mixtures may be sufficient.

As the thermoplastic resin, polyamide is preferable, nylon 6, nylon 66, derivatives or copolymers thereof, or a mixture containing any of the above, more preferably nylon 6, nylon 66.
The thermoplastic resin is also preferably a polyolefin, more preferably polyethylene, polypropylene, derivatives or copolymers thereof, or a mixture containing any of the above, and further preferably polyethylene or polypropylene.
Furthermore, an acrylonitrile butadiene styrene copolymer, a derivative or copolymer thereof, or a mixture containing any of the above is also preferable.
Furthermore, polyphenylene sulfide, a derivative or copolymer thereof, or a mixture containing any of the above is also preferable.

  The average diameter of the island phase is preferably 10 nm to 500 μm. In addition, the average diameter of an island phase refers to the average value of the diameter when each island phase is converted into a perfect circle of the same area in the cross section of the carbon fiber composite material. In the case of a hybrid alloy carbon fiber composite resin having an average diameter of the island phase of 1 μm or more, the average diameter is preferably 1 μm to 500 μm, and more preferably 1 μm to 100 μm. In the case of a hybrid nanoalloy carbon fiber composite resin having an average island phase diameter of less than 1 μm, the average diameter is preferably 10 nm to 1 μm, more preferably 50 nm to 1 μm, and more preferably 150 nm to 1 μm. Further preferred.

  In the kneading, it is preferable to use a uniaxial or biaxial extruder. Further, a vacuum vent is preferably provided in the latter half of the cylinder of the extruder, and more preferably a gear pump is provided at the tip of the extruder.

  In the method for producing the carbon fiber composite material, carbon fibers can be further added to the molten pellets and the second thermoplastic resin. Thereby, the content rate of the carbon fiber in a carbon fiber composite material can be raised, and intensity | strength can be improved. Examples of the method for adding the carbon fiber include a method for directly supplying the carbon fiber filament drawn from the carbon fiber roving to the extruder, and a method for supplying the carbon fiber cut to an appropriate length to the extruder. However, it is not limited to these.

  The carbon fiber composite material is suitable for molding applications. That is, a molded product excellent in mechanical strength and workability can be obtained by melting the carbon fiber composite material and then molding the carbon fiber composite material. In particular, the above carbon fiber composite material made of carbon fiber and thermoplastic resin is suitable for extrusion molding in which it was difficult to suppress problems such as springback in the prior art, and both the melt extrusion method and the solidification extrusion method are suitable. Available. Moreover, the said carbon fiber composite material can be used suitably also for the conventional injection molding.

  The molding method is not particularly limited. For example, a mandrel manufacturing method described in JP-A-4-152122, a resin mandrel extrusion molding apparatus, and a melt extrusion synthesis described in JP-A-2001-315193 are disclosed. Manufacturing method of resin pipe, solidified extrusion molding method described in JP 2000-313052 A and manufacturing apparatus thereof, manufacturing method and apparatus of uneven thickness resin sheet described in JP 2008-246865 A, etc. Using the known means, a molded product made of the carbon fiber composite material can be obtained. In addition, the shape of the molded product can be adjusted to a desired shape by performing heating, cooling, decompression (vacuum decompression), heat insulation and the like around the die.

  Furthermore, the molded product made of the carbon fiber composite material obtained by the above-described molding method can be further subjected to secondary processing to be remolded into a target shape. Secondary processing methods include, for example, different material lamination, same material lamination, in-mold heating, out-of-mold heating, in-mold cooling, out-of-mold cooling, in-mold pressurization, out-of-mold pressurization, in-mold decompression (vacuum decompression), Examples include out-of-mold depressurization, in-mold heat bending, out-of-mold heat bending, stretching, heat insulation, and the like, and these methods may be combined.

  In addition, in the said shaping | molding, it can also shape | mold by knead | mixing another pellet to the pellet which consists of carbon fiber composite materials.

  The carbon fiber composite material may include materials other than the above-described pellets, resins, and carbon fibers. For example, a thermosetting resin for convergence of a bundle of carbon fibers or a surface treatment may be included in an amount of 1 to 10% by weight. Further, a silane coupling agent such as amino silane, epoxy silane, amide silane, azido silane, and acrylic silane, a titanate coupling agent, or a mixture thereof may be included.

  In addition, a well-known method can be used as a manufacturing method of the pellet which has a core-sheath structure. For example, an impregnation die having a resin impregnation roll is installed, and the first thermoplastic resin melted by the extruder is stored in the resin tank of the impregnation die. The opened roving-like carbon fiber is introduced into the resin tank of the impregnation die, and the carbon fiber roving is sandwiched between the impregnation rollers while the surface of the carbon fiber roving is covered with the first thermoplastic resin. The resin is impregnated into the carbon fiber roving. At this time, the carbon fiber roving is transported by pulling the carbon fiber roving by a feed roller located downstream of the resin tank. The carbon fiber roving conveyed downstream is fed into a cutting device having a cutter after the resin amount is adjusted by the die and the cross-sectional shape is adjusted. Then, by cutting the carbon fiber roving covered with the first thermoplastic resin with a cutter of a cutting device, a pellet having a core-sheath structure in which a core made of carbon fiber is covered with the first thermoplastic resin. Can be obtained. Moreover, the pellet which consists of a 2nd thermoplastic resin is added to the pellet which has the core-sheath structure obtained by this method, These pellets are knead | mixed with a twin-screw extruder, resin amount is adjusted with die | dye, cross-sectional shape After preparing the above, the pellets made of the carbon fiber composite material can be manufactured by feeding into a cutting device having a cutter and cutting.

  An additive may be added to the thermoplastic resin as long as its properties are not significantly impaired. For example, hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides or mixtures thereof are heat stabilizers, antioxidants, reinforcing materials, pigments, anti-coloring agents, weathering agents, You may add as additives, such as a flame retardant, a plasticizer, a crystal nucleating agent, and a mold release agent.

  In the above molding, the molding process may be performed a plurality of times. For example, as the above-described molding method, a carbon fiber composite material is once molded to form an intermediate molded body, and then the obtained intermediate molded body is further molded by a press molding method, a vacuum molding method, or a blow molding method. The method of manufacturing can be adopted. Moreover, you may implement combining a some shaping | molding method, when shape | molding an intermediate molded object.

  In the molding step, the method for heating the mold and the carbon fiber composite material is not particularly limited, and known heating means such as an electric heater, a gas oven, a dielectric coil, and high-pressure steam can be appropriately used.

  The burrs that can be formed around the molded product may be cut off at the same time when the mold is fitted, or may be cut out by Thomson punching in a separate process. Moreover, by completely filling the mold with a carbon fiber composite material sheet having a size smaller than that of the mold, the occurrence of burrs can be suppressed.

  In the above molding, the carbon fiber composite material can be laminated and used, or can be used in combination with another material different from the carbon fiber composite material. For example, molding may be performed using a laminate formed by laminating a plurality of carbon fiber composite materials, or a laminate obtained by laminating a single or a plurality of carbon fiber composite materials with a single or a plurality of other materials. May be formed. Other materials that can be laminated include, for example, metal, glass, PTFE, polyester, fiber made of thermoplastic resin such as polyamide, base fabric, nonwoven fabric, or sheet made of thermosetting resin such as polyurethane, and thermosetting type. Examples include CFRP sheets and tapes, and two or more kinds of materials can be used in combination. Moreover, such other materials may be disposed in any layer in the laminate, and may be laminated on the upper end and / or the lower end of the laminate.

  In addition, glossy metal powder, minerals, rocks, and sands may be mixed in advance with the carbon fiber composite material.

  When the carbon fiber composite material is used by being laminated, it is preferable that the carbon fiber composite material is laminated so that the orientation direction of the carbon fiber intersects by 90 ° in consideration of the orientation state of the carbon fiber. Thus, the physical property of a molded object can be improved by adjusting the orientation direction of carbon fiber.

  Each layer of the laminate may be composed of a single substantially sheet-like carbon fiber composite material, or may be composed of a combination of a plurality of carbon fiber composite materials. For example, a plurality of strip-shaped carbon fiber composite materials can be arranged in the width direction to form one layer, or a plurality of strip-shaped carbon fiber composite materials can be combined in a lattice shape to form a layer. In particular, it is preferable to laminate a layer in which a plurality of band-like carbon fiber composite materials are arranged in the width direction while intersecting the arrangement direction of the carbon fiber composite materials by 90 °. By adopting such a configuration, it is possible to increase the thickness up and down while securing a wider area.

  Furthermore, it can also be made into a wide and long sheet of thick material by sandwiching it between upper and lower flat molds heated in advance and applying a pressure of 0.2 MPa to 100 MPa.

  When the carbon fiber composite material is molded using the above-described press molding method, for example, when hot pressing is performed, the pressure is preferably 0.2 to 100 MPa, and more preferably 1 to 50 MPa.

  Moreover, it is preferable that the temperature of a hot press is 100-370 degreeC. More specifically, the mold temperature is preferably in the range of −10 to 90 ° C., more preferably in the range of 0 to 50 ° C., based on the melting point of the thermoplastic resin contained in the carbon fiber composite material. preferable.

  The method of hot press molding is not particularly limited, but examples include the following methods. First, one or a plurality of carbon fiber composite materials are heated and melted at the above temperature, and then put into a mold, and the mold is closed and sealed. And in the state where the temperature of a metal mold | die is below melting | fusing point of a carbon fiber composite material, it pressurizes with the said pressure, opens a metal mold | die, and takes out a molded article.

  As another method of hot press molding, one or a plurality of carbon fiber composite materials are put into a mold whose mold temperature is adjusted to be equal to or lower than the melting point of the carbon fiber composite material, and the mold is closed. Subsequently, the temperature of the mold is heated to the above temperature to bring the carbon fiber composite material into a molten state and pressurized at the above pressure. At this time, the mold is sealed. Thereafter, the mold is cooled by cooling or water cooling, and after the carbon fiber composite material in the mold is solidified, the mold is opened and the molded product is taken out.

  As another method of hot press molding, one or a plurality of carbon fiber composite materials are heated at the above temperature to be in a semi-molten state, and this is put into a mold. At this time, it is preferable that only the surface of the carbon fiber composite material is in a semi-molten state. The mold is then closed, but not completely sealed, leaving the mold open. And after pressurizing with the said pressure in the state whose temperature of a metal mold | die is below melting | fusing point of a carbon fiber composite material, a metal mold | die is opened and a molded article is taken out.

  When performing such hot press molding, the shape of the carbon fiber composite material is preferably a sheet. The thickness of the sheet is preferably 0.1 to 3 mm, more preferably 0.5 to 2 mm, and even more preferably 1.0 to 1.5 mm.

  Moreover, when a metal mold | die consists of a convex metal mold | die and a concave metal mold | die corresponding to it, there is no restriction | limiting in particular about arrangement | positioning of a metal mold | die. For example, the upper mold may be a convex mold and the lower mold may be a corresponding concave mold, or vice versa.

When the carbon fiber composite material is molded using the vacuum forming method described above, the pressure is preferably 1 × 10 ^{−5 to} 0.05 MPa, more preferably 0.5 × 10 ^{−4 to} 0.05 MPa, × 10 ⁻⁴ to 1 × 10 ⁻³ MPa is more preferable.

  Moreover, it is preferable that the temperature at the time of vacuum forming is 100-370 degreeC. More specifically, the temperature is preferably in the range of −10 to 90 ° C., more preferably in the range of 0 to 50 ° C., based on the melting point of the thermoplastic resin contained in the carbon fiber composite material.

  The method of vacuum forming is not particularly limited, but examples thereof include the following methods. First, one or a plurality of carbon fiber composite materials are heated at the above temperature to be in a molten state, put into a mold, and the mold is closed. Then, in a state where the temperature of the mold is equal to or lower than the melting point of the carbon fiber composite material, after reducing the pressure at the above pressure, the mold is opened and the molded product is taken out. At this time, the pressure reduction may be performed on either the upper mold side or the lower mold side, or may be performed simultaneously on both the upper mold side and the lower mold side.

  As another method of vacuum forming, one or a plurality of carbon fiber composite materials are heated at the above temperature to be in a molten state, and this is put into a mold. Then, after raising the lower mold of the mold, suction is performed from the lower mold side at the above pressure, the mold is opened, and the molded product is taken out.

  As yet another method of vacuum forming, one or a plurality of carbon fiber composite materials are heated at the above temperature to form a molten state, which is then placed in a mold. Then, after raising the upper mold of the mold, suction is performed from the upper mold side at the above pressure, the mold is opened, and the molded product is taken out.

  When performing such vacuum forming, after the carbon fiber composite material is heated, before forming with the mold, air can be blown from below or compressed air can be used to make the forming uniform. . At this time, the shape of the carbon fiber composite material is preferably a sheet. In addition, when using compressed air, it is preferable that a pressure is 0.1-10 Mpa, and it is preferable to adjust a pressure so that a carbon fiber composite material may not be broken.

  When the carbon fiber composite material is molded using the blow molding method described above, the blow pressure is preferably 0.2 to 10 MPa, and more preferably 0.5 to 2 MPa.

  Moreover, it is preferable that the temperature at the time of blow molding is 100-370 degreeC. More specifically, the temperature is preferably in the range of −10 to 90 ° C., more preferably in the range of 0 to 50 ° C., based on the melting point of the thermoplastic resin contained in the carbon fiber composite material.

  The method of vacuum forming is not particularly limited, but examples thereof include the following methods. First, one or a plurality of sheets made of a carbon fiber composite material are heated at the above temperature to be in a semi-molten state, and then blown to spread the sheet. At this time, it is preferable that only the surface of the sheet is in a semi-molten state. Subsequently, the semi-molten sheet is put into a mold, and the mold is closed and blown. At this time, the mold is in a sealed state. And after pressurizing with the said pressure in the state whose temperature of a metal mold | die is below melting | fusing point of a carbon fiber composite material, a metal mold | die is opened and a molded article is taken out.

The bending method is not particularly limited, but examples thereof include the following methods. First, an I-shaped extrudate made of one or a plurality of carbon fiber composite materials is heated at 100 to 370 ° C. to be in a semi-molten state, fixed along the mold, and further 100 to 370 ° C. in an oven. Heat with. And after cooling to room temperature, it removes from a type | mold and takes out a molded article.
If it is difficult to bend, the bent portion or the like can be locally softened using an organic solvent and then heated to perform bending.

  Next, the present invention will be described more specifically with reference to examples. In each example and comparative example, the materials used and the methods for measuring the breaking strength are as follows.

(1) Used material (A) Carbon fiber roving / filament A carbon fiber filament having a fiber diameter of 7 μm, a count of 200 tex, and a winding length of 30,000 m is prepared. Five filaments are combined, 2% by weight of a polyurethane sizing agent is applied, and a flat belt-like carbon fiber roving is prepared.
(B) First thermoplastic resin B1: Nylon 6 (melting point: 225 ° C., viscosity at 275 ° C .: 100 poise)
B2: Nylon 66 (melting point: 255 ° C., viscosity at 305 ° C .: 250 poise)
B3: PP (melting point: 170 ° C., viscosity at 220 ° C .: 70 poise)
B4: ABS (glass transition point (softening point): 190 ° C., viscosity at 240 ° C .: 120 poise)
B5: PPS (melting point: 285 ° C., viscosity at 335 ° C .: 260 poise)
(C) Second thermoplastic resin C1: Nylon 6 (melting point: 225 ° C., viscosity at 275 ° C .: 1,100 poise)
C2: nylon 66 (melting point: 255 ° C., viscosity at 305 ° C .: 5,500 poise)
C3: PP (melting point: 170 ° C., viscosity at 220 ° C .: 1,770 poise)
C4: ABS (softening point: 190 ° C., viscosity at 240 ° C .: 2,520 poise)
C5: PPS (melting point: 255 ° C., viscosity at 335 ° C .: 8,060 poise)

(2) Measuring method of breaking strength In measuring the breaking strength (bending strength and bending elastic modulus), a Tensilon tensile tester (RTF-1360) was used according to JIS standard K7161.

[Example 1]
Hereinafter, the test conditions in each Example and Comparative Example are basically the same as those in Example 1 unless otherwise specified.
FIG. 7 shows a conventional method for producing a pellet having a core-sheath structure in which a core made of carbon fiber is covered with a thermoplastic resin. In the manufacturing method of FIG. 7, the flat belt-like carbon fiber roving 46 is sent to the extruder 60 via the defibrating device 50, and the first thermoplastic resin B1 made of nylon 6 is put into the extruder 60, The melted first thermoplastic resin 61 (B1) is discharged to the carbon fiber roving through the die 51 at a temperature of 275 ° C., thereby covering the surface of the carbon fiber roving 46 with the resin B1. After the carbon fiber roving 46 drawn out from the die 51 is passed through a squeeze bar 52 and the degree of impregnation of the resin B1 into the carbon fiber is increased, the shape is adjusted by the convergence shaping portion 53 and the cooling portion 54 To be cooled. Then, the carbon fiber roving 46 whose surface is coated with the resin B1 is cut by the strand cutter 57 including the rotary blade 58 and the fixed blade 62 while being taken up by the top roller 55 and the bottom roller 56, thereby obtaining FIG. As shown, pellet 6 (pellet 59 in FIG. 7) having a core-sheath structure in which a core made of carbon fiber is covered with nylon 6 is obtained. In addition, the content rate of the carbon fiber in the obtained pellet 6 is 30%.
The core-sheath-type carbon fiber-containing resin pellet 6 is put into a pellet supply device 42 shown in FIG. 5, and the pellet is supplied into the extruder 22 through the supply port 30 from the pellet supply path P1. Moreover, the pellet which consists of 2nd thermoplastic resin C1 is thrown into the pellet supply apparatus 43, and the said pellet is supplied in the extruder 22 through the supply port 30 from the pellet supply path P2. This second thermoplastic resin C1 is made of nylon 6 and has a higher viscosity than B1. These pellets are kneaded in an extruder 22 equipped with a motor 20 and a transmission 21 at a temperature of 275 ° C., deaerated with a vent 29, and poured into a die 26 while being metered with a gear pump 23. obtain. The obtained gut 28 is cooled by the cooling unit 24 and then cut by the strand cutter 27 to obtain hybrid pellets 1 made of nylon 6 (pellets made of a carbon fiber composite material). The carbon fiber content in the hybrid pellet 1 made of nylon 6 is 15% by weight.
The hybrid pellet was injection molded to produce a dumbbell piece having a measurement width of 10 ± 0.5 mm and a measurement length of 80 ± 2 mm. The resulting dumbbell pieces had a bending strength of 250 MPa and a flexural modulus of 10.2 GPa.

  The structure of a pellet 1 made of a carbon fiber composite material produced by the method described in Example 1 is shown in FIGS. FIG. 1 is a schematic perspective view showing a hybrid pellet 1 (a pellet made of a carbon fiber composite material) according to an embodiment of the present invention. 2 is a partially enlarged cross-sectional view for explaining the structure of the hybrid pellet 1. FIG. 2A is a schematic cross-sectional view showing the state of the cross-section 1a of the hybrid pellet 1, and FIG. It is sectional observation figure which shows the result of having observed the side cross section 1b of the hybrid pellet 1 manufactured by the method with the electron microscope. In FIG. 2B, in order to facilitate identification of the carbon fiber 2 and the island phase 3, the periphery of the carbon fiber 2 represented in black is bordered with a thin white line, and from the first thermoplastic resin. The configured island phase 3 is surrounded by a thick white line. As shown in FIG. 2, the hybrid pellet 1 has a structure in which island phases 3 composed of the first thermoplastic resin are dispersed in the sea phase 4 composed of the second thermoplastic resin. The carbon fiber 2 and the island phase 3 are uniformly dispersed in the hybrid pellet 1. According to such a carbon fiber composite material, since defects (for example, springback and voids) due to the uneven distribution of carbon fibers and thermoplastic resins are prevented in advance, the surface can be used not only in injection molding but also in extrusion molding. A molded article having a good state and excellent rigidity can be obtained.

  The structure of the pellet 6 used in the method described in Example 1 is shown in FIG. In FIG. 4, a pellet 6 made of a carbon fiber-containing resin has a core in which a core made of carbon fiber 2 is covered with a thermoplastic resin 3 (in Example 1, a first thermoplastic resin B1 made of nylon 6). Has a sheath structure. In addition, the structure of the pellet which has a core-sheath structure is not limited only to the above, A various pellet can be utilized suitably. For example, as shown in FIG. 3, a core made of carbon fiber 2 is covered with a thermoplastic resin 3, and a thermoplastic resin 4 having a higher viscosity than the thermoplastic resin 3 on the outside (for example, a second made of nylon 6). It is also possible to use the pellet 5 covered with the thermoplastic resin B2) as a raw material for the carbon fiber composite material.

[Example 2]
In the manufacturing method shown in FIG. 7, the first thermoplastic resin B2 made of nylon 66 is discharged from the extruder 60 to a flat belt-like carbon fiber roving at a temperature of 305 ° C., and the core made of carbon fiber is covered with the nylon 66. A core-sheath-type carbon fiber-containing resin pellet 6 having a core-sheath structure is obtained. The content rate of the carbon fiber in the obtained core-sheath-type carbon fiber containing resin pellet 6 is 40 weight%.
The core-sheath type carbon fiber-containing resin pellet 6 made of nylon 66 is put into the pellet supply device 42 shown in FIG. 5 and the pellet made of the second thermoplastic resin C2 is put into the pellet supply device 43. This second thermoplastic resin C2 is made of nylon 66, and has a higher viscosity than B2. These pellets are kneaded at a temperature of 305 ° C., and hybrid pellets 1 made of nylon 66 are obtained by the manufacturing method shown in FIG. The carbon fiber content in the hybrid pellet 1 made of nylon 66 is 20% by weight.

[Example 3]
In the manufacturing method shown in FIG. 7, the first thermoplastic resin B3 made of PP is discharged from the extruder 60 to a flat belt-like carbon fiber roving at a temperature of 220 ° C., and the core made of carbon fiber is covered with PP. A core-sheath type carbon fiber-containing resin pellet 6 having a sheath structure is obtained. The content rate of the carbon fiber in the obtained core-sheath-type carbon fiber containing resin pellet 6 is 20 weight%.
The core-sheath type carbon fiber-containing resin pellet 6 made of PP is put into the pellet feeder 42 shown in FIG. 5 and the pellet made of the second thermoplastic resin C3 is put into the pellet feeder 43. The second thermoplastic resin C3 is made of PP and has a higher viscosity than B3. These pellets are kneaded at a temperature of 220 ° C., and hybrid pellets 1 made of PP are obtained by the manufacturing method shown in FIG. The content of carbon fiber in the hybrid pellet 1 made of PP is 15% by weight.

[Example 4]
In the manufacturing method shown in FIG. 7, the first thermoplastic resin B4 made of ABS is discharged from the extruder 60 to a flat strip-like carbon fiber roving at a temperature of 240 ° C., and the core made of carbon fiber is covered with ABS. A core-sheath type carbon fiber-containing resin pellet 6 having a sheath structure is obtained. The content rate of the carbon fiber in the obtained core-sheath-type carbon fiber containing resin pellet 6 is 25 weight%.
The core-sheath type carbon fiber-containing resin pellet 6 made of ABS is put into the pellet supply device 42 shown in FIG. 5 and the pellet made of the second thermoplastic resin C4 is put into the pellet supply device 43. This second thermoplastic resin C4 is made of ABS, and has a higher viscosity than B4. These are kneaded at a temperature of 240 ° C., and hybrid pellets 1 made of ABS are obtained by the manufacturing method shown in FIG. The content of carbon fiber in the hybrid pellet 1 made of ABS is 15% by weight.

[Example 5]
In the manufacturing method shown in FIG. 7, the first thermoplastic resin B5 made of PPS is discharged from the extruder 60 to a flat strip-like carbon fiber roving at a temperature of 335 ° C., and the core made of carbon fiber is covered with PPS. A core-sheath type carbon fiber-containing resin pellet 6 having a sheath structure is obtained. The content rate of the carbon fiber in the obtained core-sheath-type carbon fiber containing resin pellet 6 is 30 weight%.
The core-sheath type carbon fiber-containing resin pellet 6 made of PPS is charged into the pellet supply device 42 shown in FIG. 5, and the pellet made of the second thermoplastic resin C5 is charged into the pellet supply device 43. The second thermoplastic resin C5 is made of PPS and has a higher viscosity than B5. These pellets are kneaded at a temperature of 335 ° C., and hybrid pellets 1 made of PPS are obtained by the manufacturing method shown in FIG. The carbon fiber content of the hybrid pellet 1 made of PPS is 20% by weight.

[Example 6]
In the manufacturing method shown in FIG. 7, the first thermoplastic resin B1 made of nylon 6 is discharged from the extruder 60 to a flat belt-like carbon fiber roving at a temperature of 275 ° C., and the core made of carbon fiber is covered with the nylon 6. A core-sheath-type carbon fiber-containing resin pellet having a core-sheath structure is obtained. The content rate of the carbon fiber in the obtained core-sheath-type carbon fiber containing resin pellet 6 is 30 weight%.
The core-sheath type carbon fiber-containing resin pellet 6 made of nylon 6 is put into a pellet supply device 42 shown in FIG. 5, and the pellet is supplied to the extruder 22 through the supply port 30 from the pellet supply path P1. Further, pellets made of the second thermoplastic resin C1 are put into the pellet supply device 43, and the pellets are supplied to the extruder 22 through the side feeder 25 from the pellet supply route P3 instead of the pellet supply route P2. These pellets are kneaded at a temperature of 270 ° C., and hybrid pellets 1 made of nylon 6 are obtained by the manufacturing method shown in FIG. The carbon fiber content in the hybrid pellet 1 made of nylon 6 is 20% by weight.

[Example 7]
In the manufacturing method shown in FIG. 7, the first thermoplastic resin B1 made of nylon 6 is discharged from the extruder 60 to a flat belt-like carbon fiber roving at a temperature of 275 ° C., and the core made of carbon fiber is covered with the nylon 6. A core-sheath-type carbon fiber-containing resin pellet 6 having a core-sheath structure is obtained. The content rate of the carbon fiber in the obtained core-sheath-type carbon fiber containing resin pellet 6 is 30 weight%.
The core-sheath type carbon fiber resin pellet 6 of nylon 6 is put into a pellet supply device 42 shown in FIG. 5, and the pellet is supplied into the extruder 22 through the supply port 30 from the pellet supply path P1. Further, pellets made of the second thermoplastic resin C1 are put into the pellet supply device 43, and the pellets are supplied into the extruder 22 through the side feeder 25 from the pellet supply route P3 instead of the pellet supply route P2. And these pellets are knead | mixed at the temperature of 275 degreeC, and the hybrid pellet 1 which consists of nylon 6 is obtained with the manufacturing method shown in FIG. The carbon fiber content in the hybrid pellet 1 made of nylon 6 is 20% by weight.

[Example 8]
In the manufacturing method shown in FIG. 7, the first thermoplastic resin B1 made of nylon 6 is discharged from the extruder 60 to a flat belt-like carbon fiber roving at a temperature of 275 ° C., and the core made of carbon fiber is covered with the nylon 6. A core-sheath-type carbon fiber-containing resin pellet 6 having a core-sheath structure is obtained. The content rate of the carbon fiber in the obtained core-sheath-type carbon fiber containing resin pellet 6 is 30 weight%.
The core-sheath type carbon fiber resin pellet 6 made of nylon 6 is put into a pellet supply device 42 shown in FIG. 5, and the pellet is supplied into the extruder 22 through the supply port 30 from the pellet supply path P1. Further, pellets made of the second thermoplastic resin C2 are charged into the pellet supply device 43, and the pellets are supplied into the extruder 22 through the side feeder 25 from the pellet supply route P3 instead of the pellet supply route P2. These pellets are kneaded at a temperature of 305 ° C., and hybrid pellets 1 made of nylon 6 and nylon 66 are obtained by the manufacturing method shown in FIG. The carbon fiber content in the hybrid pellet 1 is 15% by weight.

[Example 9]
In the manufacturing method shown in FIG. 7, the first thermoplastic resin B1 made of nylon 6 is discharged from the extruder 60 to a flat belt-like carbon fiber roving at a temperature of 275 ° C., and the core made of carbon fiber is covered with the nylon 6. A core-sheath-type carbon fiber-containing resin pellet 6 having a core-sheath structure is obtained. The content rate of the carbon fiber in the core-sheath type carbon fiber-containing resin pellet 6 is 35% by weight.
The core-sheath type carbon fiber resin pellet 6 made of nylon 6 is put into a pellet supply device 42 shown in FIG. 6, and the pellet is supplied into the extruder 22 through the supply port 30 from the pellet supply path P1. Moreover, the pellet which consists of a 2nd thermoplastic resin is thrown into the pellet supply apparatus 43, and the said pellet is supplied in the extruder 22 through the supply port 30 from the pellet supply path P2. Further, as shown in FIG. 6, a flat belt-like carbon fiber roving is supplied into the extruder 22 through the opening of the side feeder 25. These pellets and carbon fiber roving are kneaded at a temperature of 275 ° C., and hybrid pellets 1 made of nylon 6 are obtained by the manufacturing method shown in FIG. The content of carbon fiber in the hybrid pellet 1 made of nylon 6 is 47% by weight.

[Example 10]
Using the hybrid pellet 1 described in Example 1 above, extrusion molding was performed at a discharge rate of 200 g / min using the melt-extruded sheet manufacturing apparatus 111 shown in FIG. 9 to produce a sheet having a width of 300 mm and a thickness of 0.3 mm. .
More specifically, in the melt extruded sheet manufacturing apparatus 111 shown in FIG. 9, the molten resin material 114 extruded from the die 112 into a sheet shape passes through between the heater rolls 116, 118, 120, and is then stainless steel. The temperature is adjusted in a heating furnace 126 provided with a belt 124 and a belt heater roll 122. And the sheet | seat 129 as a melt-extrusion molded article is obtained by cut | disconnecting the sheet-shaped resin material 114 by which the temperature was adjusted with the cutter 128. FIG.
In this example, when the breaking strength of the obtained sheet 129 was measured, the bending strength in the longitudinal direction (longitudinal direction) was 231 MPa, and the bending elastic modulus was 9.8 GPa. Further, the bending strength in the transverse direction (width direction) was 212 MPa, and the flexural modulus was 9.2 GPa.

[Example 11]
Using the hybrid pellet 1 of Example 1 described above, extrusion molding was performed at a discharge rate of 50 g / min using a melt extrusion pipe manufacturing apparatus 130 shown in FIG. 10 to produce a pipe having an inner diameter of 20 mm and an outer diameter of 25 mm.
More specifically, in the melt extrusion pipe manufacturing apparatus 130 shown in FIG. 10, the resin material 114 extruded from the melt extrusion pipe die 131 in a molten state is supplied to the temperature adjustment water inlet 141 and the temperature adjustment water outlet 145. The shape is adjusted by a pipe sizing die 135 having a cooling part 139 that communicates with the cooling part 139 and cooled in a constant temperature water tank 147. Then, the melted extruded pipe 151 is obtained by cutting the cooled resin material 114 with the cutter 150 while continuously taking it with the take-up machine 149.
In this example, the obtained pipe 151 had a bending strength of 236 MPa and a bending elastic modulus of 9.6 GPa. Moreover, the cross-sectional shape of this pipe 151 is shown in FIG.

[Example 12]
Using the hybrid pellet 1 of Example 1 above, extrusion molding was performed at a discharge rate of 70 g / min using a melt extrusion solid molded product manufacturing apparatus 180 shown in FIG. 12 to produce a round bar having an outer diameter of 15 mm.
More specifically, in the melt-extruded solid product manufacturing apparatus 180 shown in FIG. 12, the resin material 114 extruded from the melt-extruded real product die 185 in a molten state is a solid-molded product sizing die 187. Then, the shape is adjusted and cooled by a constant temperature water tank 147. Then, the cooled resin material 114 is cut by the cutter 150 while being continuously taken by the take-up machine 149, thereby obtaining the actual product 188 (round bar in this embodiment) during melt extrusion. Since the other configuration of the manufacturing apparatus 180 is the same as that of the manufacturing apparatus 130 shown in FIG. 10, the same reference numerals as those in FIG.
In this example, the obtained round bar 188 had a bending strength of 241 MPa and a bending elastic modulus of 9.9 GPa. Moreover, the cross-sectional shape of this round bar 188 is shown in FIG.

[Example 13]
Using the hybrid pellet 1 of Example 1 described above, extrusion molding was performed at a discharge rate of 70 g / min using the melt extrusion modified product manufacturing apparatus 190 shown in FIG. 14, and I-shaped, H-shaped, and T-shaped modified extruded products. Produced.
More specifically, the resin material 114 extruded in the molten state from the melt-extruded profile die 191 in the melt-extruded profile manufacturing apparatus 190 shown in FIG. The shape is adjusted and cooled by the constant temperature water tank 147. Then, the cooled resin material 114 is cut by the cutter 150 while being continuously taken by the take-up machine 149, whereby a melt-extruded profile 194 is obtained. Since the other configuration of the manufacturing apparatus 190 is the same as that of the manufacturing apparatus 130 shown in FIG. 10, the same reference numerals as those in FIG.
In this example, the profile extrusion molding 194 obtained had a flexural strength of 238 MPa and a flexural modulus of 10.1 GPa. FIG. 15 shows the cross-sectional shapes of an I-type variant 197, an H-type variant 198, and a T-type variant 199.

[Example 14]
Using the hybrid pellet 1 of Example 1 described above, extrusion molding was performed at a discharge rate of 30 g / min using a solidified extruded product manufacturing apparatus 210 shown in FIG. 16 to produce an extruded block having a width of 300 mm and a thickness of 100 mm.
More specifically, in the solidified extrusion molded product manufacturing apparatus 210 shown in FIG. 16, the resin material 114 extruded in a molten state from the solidified extrusion die 212 is heated by a heating unit 213 provided with a heater 215. After that, it is cooled by a cooling unit 217 provided with a water channel 219, continuously taken up by a take-up machine 227, and becomes a solidified extruded product 230. A heat insulating material 218 is provided between the heating unit 213 and the cooling unit 217.
The extrusion block 231 obtained by the manufacturing apparatus 210 was cut to produce a dumbbell piece having a measurement width of 10 ± 0.5 mm and a measurement length of 80 ± 2 mm. The obtained dumbbell pieces had a bending strength of 275 MPa and a bending elastic modulus of 11.5 GPa. Moreover, the cross-sectional shape of the extrusion block 231 is shown in FIG.

[Example 15]
Using the hybrid pellet 1 of Example 1 described above, extrusion molding was performed at a discharge rate of 30 g / min using a round bar die in the solidified extrusion molded product manufacturing apparatus 210 shown in FIG. 16 to produce a φ150 mm round bar. .
The obtained round bar 232 had a bending strength of 265 MPa and a bending elastic modulus of 10.8 GPa. Moreover, the cross-sectional shape of the round bar 232 is shown in FIG.

[Example 16]
Using the hybrid pellet 1 made of nylon 66 and carbon fiber described in Example 2, as in Example 10, it was extruded at a discharge rate of 200 g / min in the melt-extruded sheet manufacturing apparatus 111 shown in FIG. A sheet having a width of 300 mm and a thickness of 0.6 mm was produced. The obtained sheet was free from spring back and voids, and had good shape and surface condition.

[Example 17]
Using the hybrid pellet 1 composed of PP and carbon fiber described in Example 3, as in Example 13, it was extruded at a discharge rate of 70 g / min in the melt-extruded profile manufacturing apparatus 190 shown in FIG. I-type, H-type, and T-type profile extrusions were produced. The obtained profile extrusion-molded product was free from spring back and voids, and had good shape and surface condition.

[Example 18]
Using the hybrid pellet 1 made of ABS and carbon fiber as described in Example 4, as in Example 11, it was extruded at a discharge rate of 50 g / min using a melt-extruded pipe manufacturing apparatus 130 shown in FIG. A pipe having a diameter of 21 mm and an outer diameter of 25 mm was produced. The obtained pipe was free from springback and voids, and had good shape and surface condition.

[Example 19]
Using the hybrid pellet 1 made of PPS and carbon fiber described in Example 5, as in Example 10, the melt-extruded sheet manufacturing apparatus 111 shown in FIG. A sheet having a thickness of 300 mm and a thickness of 0.5 mm was produced. The obtained sheet was free from spring back and voids, and had good shape and surface condition.

[Example 20]
Using the melt-extruded sheet of Example 10 as an intermediate molded body, a sheet was prepared by a hot press molding method as shown in FIG. Specifically, first, the melt-extruded sheet 129 obtained in Example 10 was cut with a width of 300 mm and a length of 1200 mm to prepare a sheet 129a. Then, as shown in FIG. 18 (a), a total of 16 sheets 129a are laminated in four layers, and the sheets are arranged so that the sheets of each layer intersect 90 degrees with the other adjacent sheets. Thus, a four-layer laminate 300 shown in FIG. As shown in FIG. 18 (c), this laminate 300 is placed in a mold comprising a concave mold 301 and a convex mold 302 and provided with a heater 305 and a water cooling tube 306, as shown in FIG. 18 (d). After closing the mold, pressurization was performed for 5 minutes under the conditions of a mold temperature of 250 ° C. and a pressure of 20 MPa. And after cooling a metal mold | die with the water cooling pipe | tube 306, a metal mold | die was opened as shown in FIG.18 (e), and the hot press molding sheet | seat 308 shown in FIG.18 (f) was obtained.
The dimensions of the obtained hot press-formed sheet 308 were 1200 mm in both length and width, and the thickness was 1.19 mm.

[Example 21]
Using the melt-extruded sheet of Example 10 as an intermediate molded body, a molded product was prepared by a hot press molding method as shown in FIG. Specifically, first, the melt-extruded sheet 129 obtained in Example 10 was cut with a width of 300 mm and a length of 300 mm to create a sheet 129b shown in FIG. As shown in FIG. 19 (b), it was put in a single die having a heater 305 and a water cooling tube 306. This mold was composed of a box-shaped concave mold 320 and a convex mold 321 having a shape corresponding to the box-shaped concave mold 320. Then, as shown in FIG.19 (c), the metal mold | die was closed and it pressurized for 5 minutes on the conditions of metal mold | die temperature 250 degreeC and pressure 15MPa. And after cooling a metal mold | die with the water cooling pipe | tube 306 and opening a metal mold | die as shown in FIG.19 (d), the deburring of the taken-out hot press molded object 324 is performed, and the box shown in FIG.19 (e) A hot press-formed product 325 having a shape was obtained.
The dimensions of the obtained hot press-formed product 325 were 10 mm in height, 150 mm in width, 170 mm in length, and the thickness was 0.25 mm.

[Example 22]
Using the hot press-molded sheet of Example 20 as an intermediate molded body, a molded product was prepared by a hot press molding method as shown in FIG. Specifically, first, the hot press-formed sheet 308 obtained in Example 20 was cut into a width of 300 mm and a length of 300 mm to create a sheet 308a shown in FIG. As shown in FIG. 20 (b), it was put in a single die having a heater 305 and a water cooling tube 306. This mold was composed of a box-shaped concave mold 320 and a convex mold 321 having a shape corresponding to the box-shaped concave mold 320. Subsequently, as shown in FIG. 20 (c), the mold was closed and pressurized for 5 minutes under the conditions of a mold temperature of 250 ° C. and a pressure of 15 MPa. And after cooling a metal mold | die with the water-cooling pipe | tube 306, opening a metal mold | die as shown in FIG.20 (d), the deburring of the taken-out hot press molded object 327 was performed, and the box shown in FIG.20 (e) A hot press molded product 326 was obtained.
The obtained hot press-formed product 326 had a height of 10 mm, a width of 150 mm, a length of 170 mm, and a thickness of 1.04 mm.

[Example 23]
Using the hot press-molded sheet of Example 20 as an intermediate molded body, a molded product was prepared by a hot press molding method as shown in FIG. Specifically, first, the hot press-molded sheet 308 obtained in Example 20 was cut into a width of 300 mm and a length of 300 mm to produce a sheet 308a shown in FIG. And after heating this sheet | seat 308a for 5 minutes at 245 degreeC in gas heating oven, as shown in FIG.21 (b), as shown in FIG.21 (b), the one piece which consists of the box-shaped concave mold 320 and the convex mold 321 corresponding to it. I put it in the mold. This mold was previously heated to 130 ° C. by the heater 305, and the dimensions of the molded part were 10 mm high, 150 mm wide, and 170 mm long. Then, as shown in FIG.21 (c), the metal mold | die was closed and pressurization was performed for 2 minutes with the pressure of 20 MPa. And after opening a metal mold | die as shown in FIG.21 (d), the taken-out hot press molded object 327a was deburred, and the box-shaped hot press molded product 326a shown in FIG.21 (e) was obtained. .
The dimensions of the obtained hot press-formed product 326a were 10 mm in height, 150 mm in width, 170 mm in length, and 1.09 mm in thickness.

[Example 24]
Using the hot press-molded sheet of Example 20 as an intermediate molded body, a molded product was prepared by a vacuum molding method as shown in FIG. Specifically, first, the hot press-formed sheet 308 obtained in Example 20 was cut into a width of 300 mm and a length of 300 mm to create a sheet 308a shown in FIG. For 5 minutes at 245 ° C. Subsequently, as shown in FIG. 22B, the sheet 308a is put into a single-piece vacuum forming die 342 provided with a suction hole 334, a suction port 335, and a heater 305, and the die temperature is 80 ° C. After forming the sheet 308a as shown in c), vacuum suction was performed at the suction hole 334 for 2 minutes under the condition of a pressure of 1.0 × 10 ⁻⁴ MPa. The dimensions of the molding part of this mold were 8 mm high, 140 mm wide, and 170 mm long. And after opening a metal mold | die as shown in FIG.22 (d), the taken-out vacuum forming body 346 was deburred, and the box-shaped vacuum-formed product 347 shown in FIG.22 (e) was obtained.
The obtained vacuum-formed product 347 had a height of 10 mm, a width of 150 mm, a length of 170 mm, and a thickness of 0.67 mm.

[Example 25]
Using the hot press-molded sheet of Example 20 as an intermediate molded body, a molded product was produced by a blow molding method as shown in FIG. Specifically, first, the hot press molded sheet 308 obtained in Example 20 was cut into a width of 300 mm and a length of 500 mm to prepare a sheet 308b. Subsequently, as shown in FIG. 23 (a), two sheets 308b are fixed to the sheet fixture 351 to create a sheet holder 352, and this sheet holder 352 is placed at 245 ° C. for 5 minutes with an infrared heater. After heating, it was placed in a mold heated to 155 ° C. As shown in FIG. 23 (b), this mold was composed of a concave upper mold 354 and a convex lower mold 353, and was provided with a blow port 355, a blow hole 356 and a heater 305. In addition, the dimensions of the shaping part of the upper mold 354 were 30 mm in height, 110 mm in width, and 160 mm in length, and the dimensions of the shaping part in the lower mold 353 were 10 mm in height, 110 mm in width, and 160 mm in length. After the mold was closed as shown in FIG. 23 (c), compressed air was poured from the blow hole 356 for 2 minutes at an air pressure of 1.5 MPa to perform molding. Then, after the mold is opened as shown in FIG. 23 (d), the sheet fixture 351 is removed and deburred from the blow molded product holder 357 taken out, and FIGS. 23 (e) and 23 (f) are obtained. A box-shaped blow molded product 358 shown in FIG.
The resulting blow molded article 358 had a height of 20 mm, a width of 110 mm, a length of 160 mm, and a thickness of 0.51 mm. Further, as can be seen from the cross-sectional view of the blow molded product 358 shown in FIG. 23 (f), the inside of the blow molded product 358 was hollow.

[Example 26]
Using the melt-extruded sheet of Example 10 as an intermediate molded body, a molded product was prepared by a hot press molding method as shown in FIG. Specifically, first, the melt-extruded sheet 129 obtained in Example 10 was cut into a width of 300 mm and a length of 1200 mm to prepare a sheet 129a. Then, as shown in FIG. 24 (a), a total of eight sheets 129a are stacked in two layers of four sheets, and the sheets of each layer are arranged so that the upper sheet intersects the lower sheet by 90 degrees. A glass fiber fabric 371 having a basis weight of 110 g / m ² and a thickness of 0.15 mm was placed on the uppermost surface to form a three-layer laminate 372. As shown in FIGS. 24 (b) and 24 (c), this laminate 372 is placed in a mold comprising a concave mold 301 and a convex mold 302 and having a heater 305 and a water-cooled tube 306. After the mold was closed as shown in d), the mold was pressurized for 5 minutes under the conditions of a mold temperature of 250 ° C. and a pressure of 15 MPa. And after cooling a metal mold | die with the water-cooling pipe | tube 306, a metal mold | die is opened as shown in FIG.24 (e), and the heat | fever which consists of a carbon fiber composite material and a glass fiber fabric as shown in FIG.24 (f). A press-formed sheet 375 was obtained.
The dimensions of the obtained hot press-formed sheet 375 were 1200 mm in both length and width, and the thickness was 0.72 mm.

[Example 27]
Using the melt-extruded sheet of Example 10 as an intermediate molded body, a molded product was produced by a hot press molding method as shown in FIG. Specifically, first, the melt-extruded sheet 129 obtained in Example 10 was cut into a width of 300 mm and a length of 1200 mm to prepare a sheet 129a. Then, as shown in FIG. 25 (a), a total of eight sheet materials 129a are laminated in four layers, and the sheet materials of each layer are arranged so that the upper sheet intersects the lower sheet by 90 degrees. At the same time, a thermoplastic resin sheet 377 made of polypropylene and having a thickness of 0.50 mm was disposed between the two layers to form a three-layer laminate 378. 25 (b) and 25 (c), this laminated body 372 is placed in a mold that includes a concave mold 301 and a convex mold 302 and is provided with a heater 305 and a water-cooled tube 306. After the mold was closed as shown in d), the mold was pressurized for 5 minutes under the conditions of a mold temperature of 250 ° C. and a pressure of 10 MPa. And after cooling a metal mold | die with the water-cooled pipe | tube 306, a metal mold | die is opened as shown in FIG.25 (e), and as shown in FIG.25 (f), hot press molding which consists of a carbon fiber composite material and a polypropylene. Sheet 379 was obtained.
The dimensions of the obtained hot press-formed sheet 379 were 1200 mm in both length and width, and the thickness was 1.05 mm.

[Example 28]
Using the hot press-molded sheet of Example 26 as an intermediate molded body, as shown in FIG. 26, a molded product was prepared by a hot press molding method. Specifically, first, the hot press-formed sheet 375 obtained in Example 26 was placed in a three-piece mold having a heater 305 and a water-cooled tube 306 as shown in FIG. This mold was composed of an upper mold 391 and a lower mold 392 corresponding to the upper mold 391, and the dimensions of the molded part were 5 mm in height, 140 mm in width, and 200 mm in length. Then, as shown in FIG.26 (b), the metal mold | die was closed and it pressurized for 7 minutes on the conditions of metal mold | die temperature 250 degreeC and pressure 12MPa. And after cooling a metal mold | die with the water cooling pipe | tube 306 and opening a metal mold | die as shown in FIG.26 (c), the deburring of the taken-out hot press molded object 394 was performed, and 3 shown in FIG.26 (d). A box-shaped hot press-formed product 393 was obtained.
The obtained hot press-formed product 393 had a height of 5 mm, a width of 140 mm, a length of 250 mm, and a thickness of 0.89 mm.

[Example 29]
Using the melt-extruded sheet of Example 10 as an intermediate molded product, a molded product was molded in substantially the same manner as in Example 27. Specifically, first, the melt-extruded sheet 129 obtained in Example 10 was cut into a width of 300 mm and a length of 1200 mm to prepare a sheet. Then, a total of 8 sheets are laminated in 4 layers, and each sheet is arranged so that the upper sheet intersects with the lower sheet by 90 degrees, and between these two layers, the basis weight is 90 g / A carbon fiber woven fabric having a thickness of 0.15 mm at m ² was disposed to prepare a three-layer laminate. This laminate was put into a mold composed of a concave mold and a convex mold, the mold was closed, and then pressed for 5 minutes under the conditions of a mold temperature of 250 ° C. and a pressure of 20 MPa. And after cooling a metal mold | die with the water cooling pipe | tube 306, the metal mold | die was opened and the hot press molding sheet | seat which consists of a carbon fiber composite material and a carbon fiber fabric was obtained.
The dimensions of the obtained hot press-formed sheet were 1200 mm in both length and width, and the thickness was 0.71 mm.

[Example 30]
Using the hot press-molded sheet of Example 29 as an intermediate molded body, a molded product was molded by substantially the same method as in Example 24. Specifically, first, the hot press-formed sheet obtained in Example 29 was cut into a width of 300 mm and a length of 300 mm to prepare a sheet, and this sheet was formed at 245 ° C. at 5 ° C. with two upper and lower electric infrared heaters. Heated for minutes. Subsequently, this sheet is put into a single vacuum forming mold, and after forming the sheet at a mold temperature of 80 ° C., vacuum suction is performed for 2 minutes under the condition of a pressure of 1.0 × 10 ⁻⁴ MPa. went. The dimensions of the molding part of the mold were 8 mm high, 140 mm wide, and 170 mm long. And after opening a metal mold | die, the deburring of the taken-out vacuum molded object was performed, and the box-shaped vacuum molded product was obtained.
The dimensions of the obtained vacuum molded product were height 8 mm, width 140 mm, length 170 mm, and thickness 0.61 mm.

[Example 31]
Using the hot press-molded sheet of Example 27 as an intermediate molded product, a molded product was produced by a method substantially similar to that of Example 25. Specifically, first, the hot press-formed sheet obtained in Example 20 was cut into a width of 300 mm and a length of 500 mm to prepare a sheet, and the two sheets were fixed to a sheet fixture and a sheet holder. It was created. The sheet holder was heated with an infrared heater at 245 ° C. for 5 minutes, and then placed in a mold and the mold was closed. Subsequently, air was flown for 2 minutes at a pressure of 1.5 MPa under a mold temperature of 80 ° C. to perform molding. And after opening a metal mold | die, the taken-out blow molded object was deburred and the hollow and box-shaped blow molded product was obtained.
The dimensions of the obtained blow-molded product were a height of 20 mm, a width of 110 mm, a length of 160 mm, and a thickness of 0.50 mm. Moreover, the inside of the obtained blow molded product was hollow.

[Example 32]
The profile extrudate I type 197 obtained in Example 17 was heated to 200 ° C. in an oven and bent. As shown in FIG. 27, an S-shaped bent product 401 and a square bent product 402 could be obtained.

[Comparative Example 1]
Hereinafter, the test conditions in each comparative example are basically the same as those in Example 1 unless otherwise specified.
In the manufacturing method of FIG. 7 which is a manufacturing method of pellets having a core-sheath structure in the prior art, the first thermoplastic resin B1 made of nylon 6 is discharged from the extruder 60 to a flat belt-like carbon fiber roving at a temperature of 275 ° C. Thus, a core-sheath type carbon fiber-containing resin pellet 6 having a core-sheath structure in which a core made of carbon fiber is covered with nylon 6 is obtained. The content rate of the carbon fiber in the obtained core-sheath-type carbon fiber containing resin pellet 6 is 15%.
The pellet was used for injection molding to produce a dumbbell piece similar to that in Example 1. The resulting dumbbell pieces had a bending strength of 188 MPa and a flexural modulus of 8.0 GPa.

[Comparative Example 2]
In the manufacturing method of FIG. 7 which is a manufacturing method in the prior art of a pellet having a core-sheath structure, the pellet 5 having the three-layer structure shown in FIG. 3 is manufactured by using the die 70 of FIG. . More specifically, in the die 70, the molten first thermoplastic resin 61 is discharged to the carbon fiber roving 46 through the introduction hole 72a, and the surface of the carbon fiber roving 46 is covered with the first thermoplastic resin 61. To do. Subsequently, the melted second thermoplastic resin 71 is discharged to the carbon fiber roving 46 through the introduction hole 72 b, and the surface of the first thermoplastic resin 61 is covered with the second thermoplastic resin 71. Other procedures are the same as those in the manufacturing method shown in FIG. In this comparative example, the resin B1 made of nylon 6 is used as the first thermoplastic resin, the resin B2 made of nylon 6 is used as the second thermoplastic resin, and the temperature in the die 70 is set to 275 ° C. A pellet 5 having the three-layer structure shown in FIG. 3 was obtained. The content rate of the carbon fiber in the obtained core-sheath-type carbon fiber resin pellet 5 is 15%.
The pellet was used for injection molding to produce a dumbbell piece similar to that in Example 1. The obtained dumbbell pieces had a bending strength of 210 MPa and a flexural modulus of 9.3 GPa.

[Comparative Example 3]
Further, using the core-sheath type carbon fiber-containing resin pellet 6 described in Comparative Example 1 above, a mandrel manufacturing method and extrusion molding apparatus described in JP-A-4-152122, JP-A-2001-315193 A method for producing a melt-extruded synthetic resin pipe described in the publication, a solidified extrusion molding method and a production apparatus thereof disclosed in JP 2000-313052, and JP 2008-246865 A An attempt was made to produce a molded product by known means such as a manufacturing method and apparatus for uneven thickness resin sheet, but the carbon fiber pushed the resin with low viscosity, and a molded product satisfying the quality standards as a product was obtained. I couldn't. Moreover, since dispersion | distribution of carbon fiber was inadequate, carbon fiber appeared on the surface of the obtained molded product, and the shape was also inferior.

[Comparative Example 4]
Further, using the carbon fiber-containing resin pellet 5 made of nylon 6 described in Comparative Example 2, a mandrel manufacturing method and an extrusion molding apparatus described in JP-A-4-152122, and JP-A-2001-315193 are disclosed. The method of manufacturing a melt-extruded synthetic resin pipe described in Japanese Patent Publication No. 2000-313052, the solidified extrusion manufacturing method described in Japanese Patent Application Laid-Open No. 2000-313052, and its manufacturing apparatus, and Japanese Patent Application Laid-Open No. 2008-246865 are described. An attempt was made to produce a molded article by known means such as a manufacturing method and apparatus for an uneven thickness resin sheet, but the dispersion of carbon fiber, resin B1, and resin B2 having a higher viscosity than B1 was insufficient. There was no molded product that satisfied the quality standards of the product. Moreover, since dispersion | distribution of carbon fiber was inadequate, carbon fiber appeared on the surface of the obtained molded product, and the shape was also inferior.

[Comparative Example 5]
An attempt was made to produce a sheet having a width of 300 mm and a thickness of 0.3 mm by using the pellet 6 described in Comparative Example 1 above by extrusion molding at a discharge rate of 200 g / min with the melt extrusion sheet manufacturing apparatus 111 shown in FIG. However, a sheet having the desired thickness could not be obtained, and a thickness of 0.7 mm was the limit. In addition, although a 0.7 mm thick sheet could be produced, the obtained sheet had low defibration properties and poor surface quality.

[Comparative Example 6]
The pellet 6 described in Comparative Example 1 above was extruded at a discharge rate of 50 g / min using the melt extrusion pipe manufacturing apparatus 130 shown in FIG. 10 to produce a pipe having an inner diameter of 20 mm and an outer diameter of 25 mm. As a result, springback due to carbon fiber occurred, and a desired pipe could not be produced.

[Comparative Example 7]
Using pellets 6 described in Comparative Example 1 above, extrusion molding was performed at a discharge rate of 70 g / min using a melt extrusion solid molded product manufacturing apparatus 180 shown in FIG. 12, and an attempt was made to produce a round bar having an outer diameter of 15 mm. However, the spring back by carbon fiber generate | occur | produced and the desired round bar was not able to be produced.

[Comparative Example 8]
Using the pellet 6 described in Comparative Example 1 above, extrusion molding is performed at a discharge rate of 70 g / min using the melt extrusion modified product manufacturing apparatus 190 shown in FIG. 14, and I-shaped, H-shaped, and T-shaped modified extruded products. However, a carbon fiber springback occurred, and a desired molded product could not be produced.

[Comparative Example 9]
Using the pellet 6 described in Comparative Example 1 above, extrusion molding was performed at a discharge rate of 30 g / min using a solidified extruded product manufacturing apparatus 210 shown in FIG. 16 to produce an extruded block having a width of 300 mm and a thickness of 100 mm.
The extruded block was cut to create a dumbbell piece with a measurement width of 10 ± 0.5 mm and a measurement length of 80 ± 2 mm. However, there is a void in the block, and the desired dumbbell piece can be produced. There wasn't.

[Comparative Example 10]
Using pellets 6 described in Comparative Example 1 above, extrusion molding was performed at a discharge rate of 30 g / min using the solidified extrusion molded product manufacturing apparatus 210 shown in FIG. 16 and an attempt was made to produce a φ150 mm round bar. There were many voids, and a desired round bar could not be produced.

[Comparative Example 11]
Using a nylon 6 pellet 110 containing 20% by weight of glass fiber, extrusion molding was performed at a discharge rate of 200 g / min using a melt-extruded sheet manufacturing apparatus 111 shown in FIG. 9, and the width was 300 mm and the thickness was 0.7 mm. Although an attempt was made to produce a sheet, clogging occurred, and a desired sheet could not be produced.
Therefore, this pellet was injection molded to produce a dumbbell piece similar to that in Example 1. The resulting dumbbell pieces had a bending strength of 171 MPa and a flexural modulus of 5.8 GPa.

[Comparative Example 12]
An attempt was made to produce a pipe having an inner diameter of 20 mm and an outer diameter of 25 mm by using the pellet 5 described in Comparative Example 2 by extrusion molding at a discharge rate of 50 g / min with the melt extrusion pipe manufacturing apparatus 130 shown in FIG. That is, clogging occurred, and a desired molded product could not be produced.

[Comparative Example 13]
An attempt was made to produce a round bar with an outer diameter of 15 mm by using the pellet 5 described in Comparative Example 2 by extrusion molding at a discharge rate of 70 g / min in the melt extrusion solid molded product manufacturing apparatus 180 shown in FIG. However, the obtained round bar had many voids in the cross section, and could not be stably and continuously formed.

[Comparative Example 14]
Using the pellet 5 described in Comparative Example 2, extrusion molding was performed at a discharge rate of 70 g / min using the melt extrusion profile manufacturing apparatus 190 shown in FIG. 14, and I-type, H-type, and T-type profile extrusion-molded products. Although an attempt was made to produce the molded article, the resulting molded article had many voids in the cross section, and could not be stably and continuously molded.

[Comparative Example 15]
The pellet 5 described in Comparative Example 2 was extruded at a discharge rate of 30 g / min using a solidified extruded product manufacturing apparatus 210 shown in FIG. 16 to produce an extruded block having a width of 300 mm and a thickness of 100 mm.
We tried to produce a dumbbell piece with a measurement width of 10 ± 0.5 mm and a measurement length of 80 ± 2 mm by cutting this extruded block. However, there is a void in the block, and it is possible to produce a desired dumbbell piece. could not.

[Comparative Example 16]
The pellet 5 described in Comparative Example 2 was extruded at a discharge rate of 30 g / min using a solidified extruded product manufacturing apparatus 210 shown in FIG. 16 to produce a φ150 mm round bar. When the obtained round bar was examined, voids were generated in the cross section.

[Comparative Example 17]
Extrusion block of 300 mm width and 100 mm thickness is extruded using non-reinforced pellets made of nylon 6 and containing no reinforcing fibers, with a solidified extruded product manufacturing apparatus 210 shown in FIG. 16 at a discharge rate of 30 g / min. Was made. Then, the extruded block was cut to produce a dumbbell piece, and the strength was measured. As a result, the bending strength was 106 MPa, and the bending elastic modulus was 2.7 GPa.

  The carbon fiber composite material and molded product thereof according to the present invention are suitable for all uses where high strength and excellent workability are required, and as mass-produced products such as cushioning materials, heat insulating materials, reinforcing materials, seat belts, and pipes. In addition to the above-mentioned applications, it is also suitable for applications such as samples before mold manufacture and products for the semiconductor industry, such as products for high-mix low-volume production that require high accuracy.

DESCRIPTION OF SYMBOLS 1 Pellets made of carbon fiber composite material 2 Carbon fiber 3 First thermoplastic resin 4 Second thermoplastic resin 5 Pellet having a three-layer structure 6 Pellet having a two-layer structure 20 Motor 21 Transmission 22 Extruder 23 Gear pump 24 Cooling unit 25 Side feeder 26 Die 27 Strand cutter 28 Gut 29 Vent 30 Supply port 42, 43 Pellet supply device 45 Bobbin 46 Carbon fiber roving 50 Defibration device 51 Die 52 Shigoba 53 Converging shaping unit 54 Cooling unit 55 Bottom roller 56 Top Roller 57 Strand cutter 58 Rotary blade 60 Extruder 61 First thermoplastic resin 62 Fixed blade 70 Die 71 Second thermoplastic resin 72a, 72b Introduction hole 75 Pellet 111 Molten extruded sheet manufacturing apparatus 112 Die 114 Carbon fiber composite material 116, 118, 20 Heater Roll 122 Belt Heater Roll 124 Stainless Steel Belt 126 Heating Furnace 128 Cutter 129, 129a, 129b Sheet 130 Melting Extrusion Pipe Production Equipment 131 Melting Extrusion Pipe Die 135 Pipe Sizing Die 139 Cooling Unit 141 Temperature Control Water Inlet 145 Temperature Controlled water outlet 147 Constant temperature water tank 149 Take-out machine 150 Cutter 151 Melt extrusion pipe 180 Melt extrusion production device 185 for actual molded product 187 Melt extrusion middle molded product die 187 Solid molded product sizing die 188 Melt extrusion actual product 190 Melting Extruded profile manufacturing device 191 Melt extrusion profile die 192 Profile profile sizing die 194 Melt extrusion profile 197 I profile profile 198 H profile profile 199 T profile profile 210 Solid extrusion product manufacturing system 212 Solid extrusion Die for molded products 213 Heating unit 215 Heater 217 Cooling unit 218 Heat insulating material 219 Water passage 227 Take-up machine 230 Solidified extruded product 231 Block 232 Round bar 300 Laminated body 301 Concave die 302 Convex die 305 Heater 306 Water cooling pipes 308, 308a, 308b Hot press molding Sheet 320 Box-shaped concave mold 321 Box-shaped convex molds 324, 327, 327a, 394 Hot press molded bodies 325, 326, 326a, 375, 379, 393 Hot press molded products 342 Vacuum molding mold 344 Suction hole 345 Suction port 346 Vacuum molded body 347 Vacuum molded product 351 Sheet fixture 352 Sheet holder 353,392 Lower mold 354,391 Upper mold 355 Blow port 356 Blow molded product holder 358 Blow molded product 371 Glass fiber fabric 372 378 Laminate 377 Thermoplastic Tree Sheet 401 S-shaped bent parts 402 quadrangular bent products P1, P2, P3 pellet supply path

(1) A pellet having a core-sheath structure in which the core component is made of carbon fiber and the sheath component is made of the first thermoplastic resin and the second thermoplastic resin are melted, and the molten pellet and the second thermoplastic resin are melted. in the method of producing a carbon fiber composite material is kneaded at a predetermined temperature, the second thermoplastic resin, viscosity than the first thermoplastic resin at a predetermined temperature is rather high, the first thermoplastic resin at a predetermined temperature The method for producing a carbon fiber composite material is characterized in that the viscosity of the second thermoplastic resin at a predetermined temperature is 50 to 500 poise, and the viscosity of the second thermoplastic resin is 1,000 to 10,000 poise .
(2) The method for producing a carbon fiber composite material according to (1), wherein the viscosity of the second thermoplastic resin is 10 to 750 times the viscosity of the first thermoplastic resin at a predetermined temperature.
( 3 ) The carbon fiber according to (1) or (2) , wherein the predetermined temperature is higher than the melting point of the second thermoplastic resin, and the difference between the predetermined temperature and the melting point of the second thermoplastic resin is 30 to 90 ° C. A method for producing a composite material.
( 4 ) The method for producing a carbon fiber composite material according to any one of (1) to ( 3 ), wherein the melting point of the second thermoplastic resin is 100 to 370 ° C.
( 5 ) The method for producing a carbon fiber composite material according to any one of (1) to ( 4 ), wherein carbon fibers are further added to the melted pellets and the second thermoplastic resin.
( 6 ) The method for producing a carbon fiber composite material according to any one of (1) to ( 5 ), wherein the carbon fiber composite material contains carbon fiber in a proportion of 5 to 60% by weight.
( 7 ) A method for producing a molded product, comprising melting a carbon fiber composite material produced by the method for producing a carbon fiber composite material according to any one of (1) to ( 6 ) and then molding the carbon fiber composite material.
( 8 ) The method for producing a molded article according to ( 7 ), wherein the carbon fiber composite material is molded by a melt extrusion method or a solidification extrusion method.
(9) forming a preform by molding the carbon fiber composite material, the intermediate product further press molding method, vacuum molding method, molding by blow molding or bending, of the molded article (7) Production method.
( 10 ) The method for producing a molded article according to ( 9 ), wherein the intermediate molded body is hot-pressed under conditions of a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 ° C.
( 11 ) The method for producing a molded article according to ( 9 ), wherein the intermediate molded body is vacuum-molded under conditions of a pressure of 1 × 10 ^{−5 to} 0.05 MPa and a temperature of 100 to 370 ° C.
( 12 ) The method for producing a molded article according to ( 9 ), wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.
( 13 ) The method for producing a molded product according to any one of (9) to (12) , wherein the intermediate molded body is molded in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric, or a carbon fiber composite material. .
( 14 ) An island phase composed of the first thermoplastic resin is formed in the sea phase composed of the first thermoplastic resin, the second thermoplastic resin and the carbon fiber, and composed of the second thermoplastic resin. the dispersed structure possess, in a temperature range of the melting point + 90 ° C. of the second thermoplastic resin melting point + 30 ° C. ~ second thermoplastic resin, the viscosity of the first thermoplastic resin is at 50~500poise A carbon fiber composite material , wherein the second thermoplastic resin has a viscosity of 1,000 to 10,000 poise .
( 15 ) The carbon fiber composite material according to ( 14 ), wherein the refractive index of the first thermoplastic resin is different from the refractive index of the second thermoplastic resin.
( 16 ) The carbon fiber composite material according to (14) or (15) , wherein 50% by weight or more of the carbon fibers contained in the carbon fiber composite material is present in the island phase.
( 17 ) The carbon fiber composite material according to any one of (14) to (16) , comprising carbon fiber in a proportion of 5 to 60% by weight.
( 18 ) The carbon fiber composite material according to any one of (14) to (17) , wherein an average diameter of the island phase is 10 nm to 100 μm.
( 19 ) The carbon fiber composite material of ( 18 ), wherein the average diameter of the island phase is 10 nm to 1 μm.
( 20 ) A molded product formed by molding the carbon fiber composite material according to any one of (14) to (19) .
( 21 ) A molded article according to ( 20 ), which is molded by a melt extrusion method or a solidification extrusion method.
( 22 ) Forming an intermediate molded body by molding a carbon fiber composite material, and then molding the intermediate molded body by press molding, vacuum molding, blow molding or bending. ( 20 ) Goods.
( 23 ) The molded article according to ( 22 ), wherein the intermediate molded body is hot-pressed under conditions of a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 ° C.
( 24 ) The molded article according to ( 22 ), wherein the intermediate molded body is vacuum-molded under conditions of a pressure of 1 × 10 ^{−5 to} 0.05 MPa and a temperature of 100 to 370 ° C.
( 25 ) The molded article according to ( 22 ), wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.
( 26 ) The molded article according to any one of (22) to (25) , wherein the intermediate molded body is molded in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric, or a carbon fiber composite material.

Further, in the above predetermined temperature, the viscosity of the first thermoplastic resin is a 50～500Poise, the viscosity of the second thermoplastic resin is Ru 1,000~10,000poise der. Furthermore, at the predetermined temperature, it is more preferable that the viscosity of the first thermoplastic resin is 100 to 300 poise and the viscosity of the second thermoplastic resin is 1,500 poise to 5000 poise.

(1) A pellet having a core-sheath structure in which the core component is made of carbon fiber and the sheath component is made of the first thermoplastic resin and the second thermoplastic resin are melted, and the molten pellet and the second thermoplastic resin are melted. In the method for producing a carbon fiber composite material in which the second thermoplastic resin is kneaded at a predetermined temperature, the second thermoplastic resin has a viscosity higher than that of the first thermoplastic resin at the predetermined temperature, and the first thermoplastic resin at the predetermined temperature. viscosity of 50～500Poise, the viscosity of the second thermoplastic resin at a given temperature Ri 1,000~10,000poise der higher than the predetermined temperature of the second thermoplastic resin melting point, wherein the predetermined the method of producing a carbon fiber composite material difference between the temperature and the melting point of the second thermoplastic resin is characterized by 30 to 90 ° C. der Rukoto.
(2) The method for producing a carbon fiber composite material according to (1), wherein the viscosity of the second thermoplastic resin is 10 to 750 times the viscosity of the first thermoplastic resin at a predetermined temperature.
( 3 ) The method for producing a carbon fiber composite material according to (1) or (2) , wherein the melting point of the second thermoplastic resin is 100 to 370 ° C.
( 4 ) The method for producing a carbon fiber composite material according to any one of (1) to ( 3 ), wherein carbon fiber is further added to the melted pellet and the second thermoplastic resin.
( 5 ) The method for producing a carbon fiber composite material according to any one of (1) to ( 4 ), wherein the carbon fiber composite material contains carbon fiber in a proportion of 5 to 60% by weight.
( 6 ) A method for producing a molded article, comprising melting a carbon fiber composite material produced by the method for producing a carbon fiber composite material according to any one of (1) to ( 5 ), and then molding the carbon fiber composite material.
( 7 ) The method for producing a molded article according to ( 6 ), wherein the carbon fiber composite material is molded by a melt extrusion method or a solidification extrusion method.
(8) forming a preform by molding the carbon fiber composite material, the intermediate product further press molding method, vacuum molding method, molding by blow molding or bending, of the molded article (6) Production method.
( 9 ) The method for producing a molded article according to ( 8 ), wherein the intermediate molded body is hot-pressed under conditions of a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 ° C.
( 10 ) The method for producing a molded article according to ( 8 ), wherein the intermediate molded body is vacuum-molded under conditions of a pressure of 1 × 10 ^{−5 to} 0.05 MPa and a temperature of 100 to 370 ° C.
( 11 ) The method for producing a molded article according to ( 8 ), wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.
( 12 ) The method for producing a molded article according to any one of ( 8 ) to ( 11 ), wherein the intermediate molded body is molded in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric, or a carbon fiber composite material. .
( 13 ) An island phase composed of the first thermoplastic resin is formed in the sea phase composed of the first thermoplastic resin, the second thermoplastic resin, and the carbon fiber, and composed of the second thermoplastic resin. The viscosity of the first thermoplastic resin is 50 to 500 poise within the entire temperature range of the melting point of the second thermoplastic resin + 30 ° C. to the melting point of the second thermoplastic resin + 90 ° C. , and the said viscosity of the second thermoplastic resin is Ri 1,000~10,000poise der, carbon fiber composite which more than 50 wt% of said carbon fibers is characterized that you present in the island Aiuchi material.
(14) The carbon fiber composite material according to (13), wherein the carbon fiber and the island phase are uniformly dispersed in the sea phase.
(15) The carbon fiber composite material according to (13) or (14), wherein the refractive index of the first thermoplastic resin is different from the refractive index of the second thermoplastic resin.
( 16 ) The carbon fiber composite material according to any one of (13) to (15) , comprising carbon fiber at a ratio of 5 to 60% by weight.
(17) The carbon fiber composite material according to any one of (13) to (16) , wherein an average diameter of the island phase is 10 nm to 100 μm.
( 18 ) The carbon fiber composite material according to ( 17 ), wherein the average diameter of the island phase is 10 nm to 1 μm.
( 19 ) A molded product formed by molding the carbon fiber composite material of any one of ( 13 ) to ( 18 ).
( 20 ) The molded article according to ( 19 ), which is molded by a melt extrusion method or a solidification extrusion method.
( 21 ) After forming a carbon fiber composite material to form an intermediate molded body, the intermediate molded body is further molded by press molding, vacuum molding, blow molding or bending, ( 19 ) Goods.
(22) intermediate product is heat-pressed under a pressure 0.2~100MPa and temperature one hundred to three hundred seventy ° C., molded article (21).
( 23 ) The molded article according to ( 21 ), wherein the intermediate molded body is vacuum-molded under conditions of a pressure of 1 × 10 ^{−5 to} 0.05 MPa and a temperature of 100 to 370 ° C.
( 24 ) The molded article according to ( 21 ), wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.
( 25 ) The molded article according to any one of (21) to (24) , wherein the intermediate molded body is molded in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric, or a carbon fiber composite material.

From the viewpoint of ensuring affinity between the carbon fibers and the resin, more than 50 wt% of the carbon fibers contained in the carbon fiber composite material that exists in the island phase. Further, the ratio of the carbon fibers present in the island phase is more preferably 70% by weight or more, and further preferably 90% by weight or more.

Predetermined temperature above the melting point of the second thermoplastic resin (when the second thermoplastic resin is amorphous, the glass transition temperature) have higher than. The difference between the predetermined temperature and the melting point of the second thermoplastic resin is preferably 30 to 90 ° C, and more preferably 40 to 90 ° C.

Further, in the above predetermined temperature, the viscosity of the first thermoplastic resin is a 50～500Poise, the viscosity of the second thermoplastic resin is Ru 1,000~10,000poise der. Furthermore, at the predetermined temperature, it is more preferable that the viscosity of the first thermoplastic resin is 100 to 300 poise and the viscosity of the second thermoplastic resin is 1,500 poise to 5000 poise.

(1) A pellet having a core-sheath structure in which the core component is made of carbon fiber and the sheath component is made of the first thermoplastic resin and the second thermoplastic resin are melted, and the molten pellet and the second thermoplastic resin are melted. In the method for producing a carbon fiber composite material in which the second thermoplastic resin is kneaded at a predetermined temperature, the second thermoplastic resin has a viscosity higher than that of the first thermoplastic resin at the predetermined temperature, and the first thermoplastic resin at the predetermined temperature. The viscosity is 50 to 500 poise, the viscosity of the second thermoplastic resin at a predetermined temperature is 1,000 to 10,000 poise, the predetermined temperature is higher than the melting point of the second thermoplastic resin, and the predetermined temperature And the difference between the melting point of the second thermoplastic resin and the melting point of the second thermoplastic resin is 30 to 90 ° C.
(2) The method for producing a carbon fiber composite material according to (1), wherein the viscosity of the second thermoplastic resin is 10 to 750 times the viscosity of the first thermoplastic resin at a predetermined temperature.
(3) The method for producing a carbon fiber composite material according to (1) or (2), wherein the melting point of the second thermoplastic resin is 100 to 370 ° C.
(4) The method for producing a carbon fiber composite material according to any one of (1) to (3), wherein carbon fibers are further added to the melted pellets and the second thermoplastic resin.
(5) The method for producing a carbon fiber composite material according to any one of (1) to (4), wherein the carbon fiber composite material contains 5 to 60% by weight of carbon fiber.
(6) A method for producing a molded product, comprising melting a carbon fiber composite material produced by the method for producing a carbon fiber composite material according to any one of (1) to (5), and then molding the carbon fiber composite material.
(7) The method for producing a molded article according to (6), wherein the carbon fiber composite material is molded by a melt extrusion method or a solidification extrusion method.
(8) After forming the carbon fiber composite material to form an intermediate molded body, the intermediate molded body is further molded by a press molding method, a vacuum molding method, a blow molding method, or a bending process. Production method.
(9) The method for producing a molded article according to (8), wherein the intermediate molded body is hot-pressed under conditions of a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 ° C.
(10) The method for producing a molded article according to (8), wherein the intermediate molded body is vacuum molded under conditions of a pressure of 1 × 10 ^{−5 to} 0.05 MPa and a temperature of 100 to 370 ° C.
(11) The method for producing a molded article according to (8), wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.
(12) The method for producing a molded article according to any one of (8) to (11), wherein the intermediate molded body is molded in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric, or a carbon fiber composite material. .
(13) The pellet having the core-sheath structure in which the core component is made of carbon fiber and the sheath component is made of the first thermoplastic resin and the second thermoplastic resin are melted, and the pellet and the second heat that are melted A carbon fiber composite material obtained by kneading a plastic resin at a predetermined temperature, wherein an island phase composed of the first thermoplastic resin is dispersed in a sea phase composed of the second thermoplastic resin. The viscosity of the first thermoplastic resin is 50 to 500 poise within the entire temperature range of the melting point of the second thermoplastic resin + 30 ° C to the melting point of the second thermoplastic resin + 90 ° C, the viscosity of the second thermoplastic resin is Ri 1,000~10,000poise der, wherein the predetermined temperature is higher than the melting point of the second thermoplastic resin, of the predetermined temperature and the second thermoplastic resin The difference from the melting point is 30-90 ° C Carbon fiber composite material, characterized in that.
(14) The carbon fiber composite material according to (13), wherein the carbon fiber and the island phase are uniformly dispersed in the sea phase.
(15) The carbon fiber composite material according to (13) or (14), wherein the refractive index of the first thermoplastic resin is different from the refractive index of the second thermoplastic resin.
(16) The carbon fiber composite material according to any one of (13) to (15), comprising carbon fiber at a ratio of 5 to 60% by weight.
(17) The carbon fiber composite material according to any one of (13) to (16), wherein an average diameter of the island phase is 10 nm to 100 μm.
(18) The carbon fiber composite material according to (17), wherein the average diameter of the island phase is 10 nm to 1 μm.
(19) A molded product formed by molding the carbon fiber composite material according to any one of (13) to (18).
(20) The molded article according to (19), which is molded by a melt extrusion method or a solidified extrusion method.
(21) The molding according to (19), wherein after forming a carbon fiber composite material to form an intermediate molded body, the intermediate molded body is further molded by press molding, vacuum molding, blow molding or bending. Goods.
(22) The molded article according to (21), wherein the intermediate molded body is hot-pressed under conditions of a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 ° C.
(23) The molded article according to (21), wherein the intermediate molded body is vacuum-molded under conditions of a pressure of 1 × 10 ^{−5 to} 0.05 MPa and a temperature of 100 to 370 ° C.
(24) The molded article according to (21), wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.
(25) The molded article according to any one of (21) to (24), wherein the intermediate molded body is molded in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric, or a carbon fiber composite material.

Moreover, this invention also provides the carbon fiber composite material manufactured by the said manufacturing method. That is, the carbon fiber composite material in the present invention was melted by melting the pellet having the core-sheath structure in which the core component is made of carbon fiber and the sheath component is made of the first thermoplastic resin, and the second thermoplastic resin. A carbon fiber composite material obtained by kneading the pellets and the second thermoplastic resin at a predetermined temperature, and comprising a first thermoplastic resin in a sea phase composed of the second thermoplastic resin. have a structure in which the island phase is dispersed to be, within the full temperature range of the melting point + 90 ° C. of the second thermoplastic resin melting point + 30 ° C. ~ second thermoplastic resin, the first thermoplastic resin The viscosity is 50 to 500 poise, the viscosity of the second thermoplastic resin is 1,000 to 10,000 poise, the predetermined temperature is higher than the melting point of the second thermoplastic resin, and the predetermined temperature and the Second heat The difference between the plastic resin melting point consist of, which is a 30 to 90 ° C.. Such a carbon fiber composite material is sometimes referred to as a hybrid carbon fiber composite resin or a hybrid alloy carbon fiber composite resin. In particular, an island phase having an average diameter (described later) of 1 μm or less has excellent characteristics similar to those of Nanoalloy (registered trademark), and is sometimes called a hybrid nanoalloy carbon fiber composite resin.

From the viewpoint of ensuring affinity between the carbon fibers and the resin, Rukoto least 50 wt% of the carbon fibers contained in the carbon fiber composite material be present in the island phase. Further, the ratio of the carbon fibers present in the island phase is more preferably 70% by weight or more, and further preferably 90% by weight or more.

Claims (27)

  A pellet having a core-sheath structure in which a core component is made of carbon fiber and a sheath component is made of a first thermoplastic resin and a second thermoplastic resin are melted, and the pellets and the second thermoplastic resin thus melted are melted. In the method for producing a carbon fiber composite material kneaded at a predetermined temperature, the second thermoplastic resin has a viscosity higher than that of the first thermoplastic resin at the predetermined temperature. Manufacturing method.   2. The method for producing a carbon fiber composite material according to claim 1, wherein the viscosity of the second thermoplastic resin is 10 to 750 times the viscosity of the first thermoplastic resin at the predetermined temperature.   The viscosity of the first thermoplastic resin at the predetermined temperature is 50 to 500 poise, and the viscosity of the second thermoplastic resin at the predetermined temperature is 1,000 to 10,000 poise. The manufacturing method of the carbon fiber composite material of description.   The predetermined temperature is higher than the melting point of the second thermoplastic resin, and a difference between the predetermined temperature and the melting point of the second thermoplastic resin is 30 to 90 ° C. The manufacturing method of the carbon fiber composite material of description.   The manufacturing method of the carbon fiber composite material in any one of Claims 1-4 whose melting | fusing point of a said 2nd thermoplastic resin is 100-370 degreeC.   The method for producing a carbon fiber composite material according to any one of claims 1 to 5, wherein carbon fibers are further added to the melted pellets and the second thermoplastic resin.   The manufacturing method of the carbon fiber composite material in any one of Claims 1-6 in which the carbon fiber is contained in the said carbon fiber composite material in the ratio of 5 to 60 weight%.   A carbon fiber composite material produced by the method for producing a carbon fiber composite material according to any one of claims 1 to 7, wherein the carbon fiber composite material is melted and then molded.   The manufacturing method of the molded article of Claim 8 which shape | molds the said carbon fiber composite material by the melt extrusion method or the solidification extrusion method.   The molded article according to claim 8, wherein after forming the carbon fiber composite material to form an intermediate molded body, the intermediate molded body is further molded by a press molding method, a vacuum molding method, a blow molding method, or a bending process. Production method.   The method for producing a molded article according to claim 10, wherein the intermediate molded body is hot-pressed under conditions of a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 ° C. The manufacturing method of the molded article of Claim 10 in which the said intermediate molded object is vacuum-molded on the conditions of pressure 1 * 10 < ^-5 > -0.05MPa and temperature 100-370 degreeC.   The method for producing a molded product according to claim 10, wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.   The manufacturing method of the molded article in any one of Claims 10-13 in which the said intermediate molded object is shape | molded in the state laminated | stacked with the thermoplastic resin material, the glass fiber base fabric, or the said carbon fiber composite material.   An island phase composed of the first thermoplastic resin is dispersed in a sea phase composed of the first thermoplastic resin, the second thermoplastic resin and the carbon fiber, and composed of the second thermoplastic resin. A carbon fiber composite material characterized by having a structure.   The carbon fiber composite material according to claim 15, wherein a refractive index of the first thermoplastic resin is different from a refractive index of the second thermoplastic resin.   The carbon fiber composite material according to claim 15 or 16, wherein 50% by weight or more of the carbon fibers contained in the carbon fiber composite material is present in the island phase.   The carbon fiber composite material according to any one of claims 15 to 17, comprising the carbon fiber in a proportion of 5 to 60% by weight.   The carbon fiber composite material according to any one of claims 15 to 18, wherein an average diameter of the island phase is 10 nm to 100 µm.   The carbon fiber composite material according to claim 19, wherein an average diameter of the island phase is 10 nm to 1 μm.   A molded product formed by molding the carbon fiber composite material according to any one of claims 15 to 20.   The molded article according to claim 21, which is molded by a melt extrusion method or a solidification extrusion method.   The molding according to claim 21, wherein after forming the carbon fiber composite material to form an intermediate molded body, the intermediate molded body is further molded by a press molding method, a vacuum molding method, a blow molding method or a bending process. Goods.   The molded article according to claim 23, wherein the intermediate molded body is hot-pressed under conditions of a pressure of 0.2 to 100 MPa and a temperature of 100 to 370 ° C. The molded article according to claim 23, wherein the intermediate molded body is vacuum-molded under conditions of a pressure of 1 x 10 ^{-5 to} 0.05 MPa and a temperature of 100 to 370 ° C.   The molded article according to claim 23, wherein the intermediate molded body is blow-molded under conditions of an air pressure of 0.2 to 10 MPa and a temperature of 100 to 370 ° C.   The molded article according to any one of claims 23 to 26, wherein the intermediate molded body is molded in a state of being laminated with a thermoplastic resin material, a glass fiber base fabric, or the carbon fiber composite materials.

Images