The name of the invention: a composite material
Technical field
[0001]
　The present invention relates to an organic continuous fiber-reinforced thermoplastic resin composite material, particularly suitable composite material application and member impact resistance is required, and a sandwich material for the composite material and the core material.
Background technique
[0002]
　Plastic, in particular it can be processed by thermoplastic various molding methods, a material which is indispensable for our life today. However, the flexibility of the thermoplastic resin, in some cases leads to low strength and stiffness, high strength, in applications requiring high rigidity, reinforcement by short fibers of inorganic fibers such as glass fiber or carbon fiber line have we. However, composite such as a thermoplastic resin and inorganic glass fiber which is the organic matter are difficult to recycle, there is a problem of disposal surface. The glass fibers are heavy because of the high specific gravity, there is a problem that unsuitable for weight reduction. Moreover, reinforcement by inorganic fibers, although effective in improving the strength and rigidity of the composite material, there is no much effect on the performance such as impact resistance.
　Therefore, study of the complexed by a thermoplastic resin and an organic fiber have been made. For example, in Patent Document 1, in order to improve the strength, it has been proposed to composite while pushing the organic fibers of the long fiber, which aligned in the thermoplastic resin in a molten state was discharged from the extruder by a roller. In Patent Document 2, less than the tensile modulus 1 GPa, by complexing the fabric elongation 300% or more thermoplastic elastomers and silk fibers, have been proposed to improve the impact resistance of the resin composition .
　On the other hand, rubber or EPDM, such as latex (ethylene - propylene copolymer) rubber materials reinforced thermoplastic elastomer in an organic fiber such as is used in applications of the tire, hoses, such as a belt.
　Further, as described in Patent Document 1, such as strength of the composite material can be improved by the effect of the organic fiber. However, a significant feature is the impact resistance of the organic fiber. In Patent Document 1, it has not been studied about this impact. In Patent Document 2, although improved the impact resistance of composite materials using silk fibers, silk fibers has a problem in productivity because of the natural fibers, the economics of such cost because it is expensive also there is a problem. Natural fibers such as silk fibers as compared to the synthetic fibers, generally strength was also a problem that low.
　Further, composite materials reinforced with rubber and thermoplastic elastomers in organic fibers, since rubber or thermoplastic elastomer as the matrix is flexible, there is no problem in impact resistance, low hardness and elastic modulus.
Patent Document 1: Japanese Unexamined Patent Publication No. 2002-144395
Patent Document 2: Kohyo 2009-530469 JP
Disclosure of the Invention
Problems that the Invention is to Solve
[0003]
　The present invention has been made in consideration of such conventional problems, applications where impact resistance is required, suitable for members, and recyclability, lightness, productivity, excellent organic filament in economics and to provide a composite material comprising a thermoplastic resin.
Means for Solving the Problems
[0004]
　The present inventors have result of intensive investigation to achieve the above object, by complexing with the thermoplastic resin using organic filaments having a melting point of 200 ° C. or higher, it can solve the above problems, including the recyclability It was. That is, the present invention provides a composite material having a melting point consists of between 200 ℃ and 500 ℃ organic filaments and the thermoplastic resin, the form of the organic filament is a twisted yarn cord or fabric or knitted fabric composed of twisted yarn cord, composite material characterized molded article therefrom, and a sandwich material for the composite material and the core material.
Effect of the invention
[0005]
　The present invention, high-strength, while maintaining a high elastic modulus, a composite material the impact resistance is required, it is possible to provide good economy. Also composite materials of the present invention is lightweight, productivity, is excellent in recyclability. Also from the composite material of the present invention can provide a molded article, preferably the shock-absorbing material can be provided. Also by a sandwich material for the core material of the composite material, high strength, high rigidity shock absorbing material is a molded article can provide, automotive parts structural materials, automobile parts exterior materials, automotive interior it can be preferably used as a component for the wood.
Brief description of the drawings
[0006]
　Figure 1 is a cross-sectional photograph of a composite material of Example 1 (1000-fold).
　Figure 2 is a cross-sectional photograph of a composite material of Comparative Example 6 (1000-fold).
　3 is a schematic view showing a method of measuring high-speed punching test in Examples.
BEST MODE FOR CARRYING OUT THE INVENTION
[0007]
　Hereinafter, sequentially described embodiments of the present invention.
[Organic long fiber]
　Examples of the organic filament the melting point to be used is 200 ° C. or higher in the present invention, such as polyether ether ketone fibers, polyphenylene sulfide fibers, polyether sulfone fibers, aramid fibers, polybenzoxazole fibers, polyarylate fibers, polyketone fibers, polyester fibers, polyamide fibers, such as polyvinyl alcohol fibers, and the like. Organic filament is not used as reinforcement of the composite material, in particular molding temperature resins useful in the thermoplastic resin as a matrix of the composite material, because the exception is 170. ° C. or higher, organic long fiber has a melting point of use of not less than 200 ℃. The melting point of the organic filament composite material will be melted together with the thermoplastic resin can not be obtained by mass or less forming temperature. Also, in the molding process, which is not preferable as a reinforcing material that organic long fibers to thermal degradation big. In general, since it tends to be relaxed orientation and crystallinity of the polymer in an organic length the fiber in the vicinity of the melting point, it is preferable that the melting point of the organic filament high 10 ° C. or higher than the molding temperature. The melting point of the organic fiber length is more preferable if higher 20 ℃ higher than the molding temperature.
　Although the molding temperature of the general-purpose plastics such as polyolefins are most often used in the thermoplastic resin belongs is usually 170. ° C. or higher, more heat resistance is high polyamides, polycarbonates, molding temperature engineering plastics such as polyester is 230 ℃ or more. From this, if the melting point of the organic filaments for use in the present invention is 250 ° C. or higher, it can also be used in engineering plastics as well as general-purpose plastics, and more preferably.
　Here, the melting point of 200 ° C. or higher is a sense that it does not melt below 200 ° C., but substantially even those that have no melting point, organic filaments having a melting point are preferred, the melting point substantial upper limit is 350 ℃.
　In the present invention, the melting point is also in the 200 ℃ or more organic long fiber, polyester filament, polyamide long fibers, polyvinyl alcohol long fibers preferably have a balance between the physical properties and the price, such as mechanical properties and heat resistance, among them polyester filament or nylon filaments are particularly preferred.
　As the skeleton of polyester filament, polyalkylene naphthalene dicarboxylate, polyalkylene terephthalates, such stereocomplex-type polylactic acid. Among these, polyalkylene naphthalene dicarboxylate and a polyalkylene terephthalate preferably has a melting point is 250 ℃ or more. These may be used alone or in admixture of two or more kinds may be used in the copolymerization.
　Polyalkylene naphthalene dicarboxylate, polyesters of alkylene-2,6-naphthalene dicarboxylate or alkylene-2,7-naphthalene dicarboxylate as a main recurring unit is preferred. The content of the alkylene naphthalene dicarboxylate in the polyester is preferably 90 mol% or more, more preferably 95 mol% or more, more preferably 96-100 mol%. The alkylene group, an aliphatic alkylene group may be either alicyclic alkylene group, preferably an alkylene group having 2 to 4 carbon atoms, polyalkylene naphthalene dicarboxylate is preferably polyethylene naphthalene dicarboxylate, more preferably polyethylene-2,6-naphthalene dicarboxylate.
　Polyalkylene terephthalate, alkylene - polyester terephthalate as main repeating units are preferred. The content of the alkylene terephthalate in the polyester is preferably 90 mol% or more, more preferably 95 mol% or more, more preferably 96-100 mol%. The alkylene group, an aliphatic alkylene group may be either alicyclic alkylene group, preferably an alkylene group having 2 to 4 carbon atoms, polyalkylene terephthalate is preferably polyethylene terephthalate.
　During all the repeating units of polyester fibers, Sashitsukaenai also include a third component in a range that does not impair the object of the present invention. Compounds according as the third component with (a) 2 one ester-forming functional group, such as oxalic acid, succinic acid, sebacic acid, aliphatic dicarboxylic acids such as dimer acid, cyclopropane dicarboxylic acid, hexahydro terephthalic acid alicyclic dicarboxylic acids, phthalic acid, isophthalic acid, naphthalene-2,7-dicarboxylic acid, aromatic dicarboxylic acids such as diphenyl carboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulphonic acid, diphenoxyethane carboxylic acid, 3,5 carboxylic acids such as dicarboxy sodium benzenesulfonate, glycolic acid, p- hydroxybenzoic acid, p- oxyethoxy oxycarboxylic acids such as benzoic acid, propylene glycol, trimethylene glycol, diethylene glycol, tetramethylene glycol, hexamethylene glycol, neo pentylene glycol, p- xylene glycol, 1,4-cyclohexanedimethanol, bisphenol the A, p-, p'-dihydroxyphenyl sulfone, 1,4-bis (.beta.-hydroxyethoxy) benzene, 2,2-bis (p- β- hydroxyethoxy) propane, oxy compounds such as polyalkylene glycols, or their functional derivatives, the carboxylic acid, oxycarboxylic acids, oxy compounds or highly polymerized compounds derived from functional derivatives thereof, (b ) compounds having one ester forming functional group, such as benzoic acid, benzyloxy benzoic acid, and the like methoxy polyalkylene glycol. Further (c) compounds having three or more ester-forming functional groups, such as glycerine, pentaerythritol, etc trimethylolpropane, polymers can be used within substantially linear. Also in these polyesters, matting agents such as titanium dioxide, phosphoric acid, phosphorous acid, may be included stabilizing agents, such as their esters.
　Nylon 66 is a nylon filament, nylon 6, polyamide 46 resin, a polyamide 610 resin include those consisting of aliphatic polyamides such. These may be used alone or may be used in combination of two or more kinds. These versatile among, preferably inexpensive nylon 66 or nylon 6 fiber, a melting point of nylon 66 fiber and more preferably at 250 ℃ or more.
　Organic long fibers in the present invention are those having a continuous length, the form of the organic filament is woven or knitted consists of twisted thread code or twisting code. Fibers of discrete length by combining the organic filaments may be used short fibers.
　It is preferable organic filaments for use in the present invention is a multifilament. In general, the organic fiber length, and the monofilament that becomes a commodity in a relatively thick single yarn one, is composed of a relatively narrow plurality of single thread, there is a multi-filament that is the bundles. Since monofilament is expensive because of its low productivity, it is used in special applications such as screen gauze, general clothing, the industrial materials multifilament is used. The composite material of the present invention, relatively inexpensive multi-filament is preferred. The number of single yarn constituting the multifilament is preferably 10000 from 2, more preferably 5000 to 50 present. Furthermore, more preferably 1000 from 100. When the single yarn number is more than the present 10,000, along with the production it is difficult, the handling of the fibers of a multi-filament is significantly worse.
　The total fineness of the organic filaments as multifilament used in the present invention is preferably 10000dtex from 100dtex, 8000dtex more preferably from 200 dtex. In addition, more preferably 5000dtex from 500dtex. When the fineness is less than 100 dtex, in order to strength of the yarn itself is decreased difficult to obtain the reinforcing effect of the composite material. When the fineness is larger than 10000 dtex, the manufacture of the yarn becomes difficult.
　In the present invention, it is preferred that the fineness of the single yarn constituting the organic filament is 1 ~ 30 dtex, more or less 25dtex the upper limit value, and particularly preferably not more than 20 dtex. It is also preferable as the lower limit value is greater than or equal to 1.5dtex. And most preferably in the range of 2 ~ 20dtex. By in such a range, it becomes easy to achieve the object of the present invention. Single yarn fineness tend to cause problems in the spinnability is less than 1dtex, fineness decreases the interfacial strength between too large fiber / resin, there is a tendency that the physical properties of the composite material is reduced.
　The tensile strength of the organic filament for use in the present invention is preferably 6 ~ 11cN / dtex. More preferably from 7 ~ 10cN / dtex. Is less than 6 cN / dtex, there is a tendency strength of the composite material obtained is too low.
　Further organic filaments of the present invention is preferably dry heat shrinkage at 180 ° C. is 20% or less. And still more preferably 18% or less. Dimensional changes of the fibers by heat during molding and exceeds 20% is increased, there is a tendency that defects are likely to occur in the molded shape of the reinforcing resin.
　The manufacturing method of the organic filament having such properties is not particularly limited. For example, it can be produced by a method of continuously stretching the undrawn yarn obtained by melt spinning after spinning, a method for temporarily winding separately stretched or without winding the undrawn yarn. The resulting fiber is superior in dimensional stability high strength. Further, the solution can be obtained organic filaments in a method for wet spinning a comprising a polymer as a raw material.
　Further, for the purpose of increasing the characteristics of the resin molded article, it may be treated the fiber surface with appropriate treatment agents. In this case, the surface of the fiber, with respect to the fiber 100 parts by weight, the surface treatment agent is 0.1 to 10 parts by weight, can it preferably deposited 0.1 to 3 parts by weight. Surface treatment agent, depending on the type of thermoplastic resin, can you selected.
[Twisting]
　form of organic filaments of the present invention, twisted yarns code multiplied by twisting, or woven or knitted fabric composed of the twisted yarn cord. Twist tightening the fiber bundle by is performed, impregnation of resin into the inside the fiber bundle can be suppressed. Although the details will be described later impregnation of the resin, the organic filaments may be multifilaments, the fibers Tabakan is preferably substantially thermoplastic resin is impregnated, and the fiber bundle inside the organic filaments it is preferred substantially thermoplastic resin is a non-impregnated.
　When the organic long fiber is a multi-filament, because original yarn supplied from the yarn-making manufacturer is in a state of non-twisted, the yarn as it is of single yarn pull aligned is disturbed at the time of processing, fiber performance is sufficiently there is unable to express fear. In addition, yarn of non-twisted is handling is poor due to the low convergence. In order to improve the pull aligned and handling of such a thread, it is effective to add a twist to the fibers. Further, twisting code plus twisted yarn is elongation that is higher than the raw yarn, it is effective with respect to the impact resistance and the like by bending fatigue resistance is increased. In addition, the single thread that make up the multi-filament by a twisting code can be close-packed of.
　There is no particular limitation to the twisted configuration may also pieces twist subjected to twisting only once organic filaments, using two or more yarns, or may be plied consists of ply-twisted and twists. In view of the strength and handling properties of the yarn, it plied is preferably easy to suppress the occurrence of Senart, in accordance with the respective configuration number seek the physical properties of the twist top and twist the bottom, may be set appropriately. Twist number of the fibers, once to 1000 times per 1 m, is defined preferably from 10 to 1000 times. Of these, considering the toughness is the product of strength and elongation of the twisting code, preferably 700 times the number of 30 times twist per 1 m, and more preferably 500 times from 50 times. If the number of twist is more than 1000 times, undesirable and to take into account the effect of reinforcing the composite material since the intensity of the twisting code is too low. In addition, it becomes extremely bad and productivity twist number is more than 1000 times. Number of ply-twisted and twisted down in twisted number range above is set, considering the suppression of Senart, it is preferable to set the twist number together under twisting the upper twist twist multiplier. It is also preferable in terms of durability twisting code that twist balanced and equal the number of ply-twisted and twists as used in tire cord.
　In the present invention, as the form of the organic filament, also be used as a one-way material as it is aligned plurality of pulling the twisted yarn cord subjected to twist the fibers, the fabric form such as woven or knitted fabric, i.e. be used as a bidirectional material possible it is. Composite material of the present invention can be unidirectional material, suitably selected by a two-way medium, respectively, used forms. Twisting code fineness of yarn, twist, and is defined by the distance or the like of the code, as further basis weight of a preferred twisted yarn cord 30 ~ 500 g / yd 2 is more preferably 50 ~ 300 g / yd 2 at is there. More of the weight per unit area of twisting code 30G / M 2 becomes smaller than, the energy absorption performance can not be obtained necessary. On the contrary, 500G / M 2 or less likely to enter the resin between the fiber bundle becomes greater than, tends to composite material is too heavy.
　The organization woven in the fabric, mention may be made ​​of plain weave, twill weave, a satin weave Rinado. Among them, the resin is a suitable plain weave that is easy impregnation is between organic long fiber bundles. Warp density of fabric, 50 this is preferably from to and five per 2.5cm consideration of the impregnation of the resin between the long-fiber bundle, and more preferably 40 present from ten. When the warp density is less than five, the yarn is eye opening is likely to occur in order to be easy to move, the handling of the fabric significantly deteriorate. Warp density becomes hard resin penetrates into between the fiber bundle becomes too narrow length between fiber bundles becomes more than 50 lines, not the composite material of interest is obtained. Weft density of fabric 50 present preferably from one per 2.5cm considering the impregnation of the resin between the long fiber bundles, forty from one are more preferred. Some of the fabric, the fabric performance is left to the warp, weft yarn is also cord fabric that has been used to suppress the extreme eye opening of the warp. Such cord fabric are used for a tire cord, but the weft is extremely small fabric is also applicable in the present invention. Than this, the weft density per 2.5cm may be one or more present. In contrast, when equal to or greater than 50 present too many warp density becomes too narrow length between fiber bundles it becomes the resin penetrates hardly to between fiber bundles, not composite objects can be obtained. Density of the warp and weft, may be either the same, of the imbalance as long as it is within the above range. Fabric of weight per unit area, ie organic long fiber fabrics more of a basis weight in the composite material, considering 1m the impregnation of the resin between the organic long fiber bundles 2 500G is preferably from 30g per, 400g and more preferably from 50g. If the basis weight is less than 30 g, the fabric strength can not be obtained the reinforcing effect of the composite material to lower. If the basis weight is more than 500 g, the length between the fibers bundle becomes narrower it becomes the resin is hard to impregnate into the inter-fiber bundles, not composite objects can be obtained.
　The knitting structure in the knitted fabric, warp knit, knitting the lateral, and the like Russell knitting. Among them, considering the strength of the knitted fabric, it is preferable easily Russell knitting and tougher tissues. Weight per unit area in the case of a knitted fabric, ie organic long fiber knit more of the mass per unit area in the composite material, considering 1m the impregnation of the resin between the organic long fiber bundles 2 500G is preferably from 30g per, 400g and more preferably from 50g. If the basis weight is less than 30 g, knitted strength can not be obtained the reinforcing effect of the composite material to lower. If the basis weight is more than 500 g, the length between the fibers bundle becomes narrower it becomes the resin is hard to impregnate into the inter-fiber bundles, not composite objects can be obtained.
Resin impregnation into fibers]
　In the present invention, although the resin is impregnated between the fiber bundles, one having a portion which the resin in the fiber bundle is not impregnated, i.e. having a low impregnation degree in fiber bundles preferable. The fiber bundle inside the organic filaments are substantially thermoplastic resin by a non-impregnated, and better physical properties can be obtained. In the composite material of the present invention, the organic filaments Tabakan is preferably substantially thermoplastic resin is a structure impregnated. When length between fiber bundles are not fully filled with resin, since a state in which a void remains between the long-fiber bundles, the strength of the composite material is reduced. In the present invention, among organic long fiber bundles and substantially resin impregnated structure refers to the void ratio between the fiber bundle is 10% or less. The verification can be carried out by microscopic observation of what and cross section weighing the weight of the sample that can calculate volume.
　Further, in the composite material of the present invention, the organic filaments bundle inside may be be substantially thermoplastic resin is impregnated not impregnated, but considering the impact resistance, less the fiber material since the considered Write flexibility is effective for energy absorption, the long-fiber bundle inside it is more preferable substantially resin is a non-impregnated. In the present invention, that the organic filaments bundle inside a multifilament are substantially resin not impregnated, the void fraction between the fiber bundle 10% or less of the composite material, the resin penetration into the inside the fiber bundle but it refers to 50% or less.
　The verification can be determined by calculating from the organic filaments taken out of the composite material, how much they can get single yarn constituting the multifilament, i.e. free single yarn rate. For example, in the case of organic long fiber consists of a single yarn of 250 lines, free single yarn rate If you take out a free single yarn of 150 pieces is next to 60%, resin impregnation rate is that the remaining 40%. Also, the resin impregnation ratio can be confirmed by microscopic observation, such as an electron microscope or an optical microscope, in particular can be obtained from the ratio of the void portion area in the cross section of the composite material.
　Figure 1 an example of a sectional photograph of the composite material of the present invention, Figure 2 shows an example of a sectional photograph of the corresponding composite material comparative example. Round shape, which is more observed in the photograph is the outline of the single yarn cross-section of the organic fiber, those circles appear tightly grouped is a fiber bundle. 're White visible on the outside of the circle is a thermoplastic resin, what appears black is void portion. 1 and the voids are observed in the interior fiber bundles, the intrudes thermoplastic resin is observed inside the fiber bundle in Fig.
　With the above structure, the strength of the composite material can be maintained by a thermoplastic resin between the organic filaments and the fiber bundle. The organic filaments in the composite material, since precisely the single yarn constituting the fiber has freedom of deformation and movement, the impact composite material received and absorbed by these degrees of freedom also involve destruction it becomes possible, an excellent material to impact resistance.
　About the resin penetration into the fiber bundle inside, twisting the above, the fabric, in addition to the knitting structure, selection of the type of the thermoplastic resin, and the pressure of the molding in the impregnation step of resin into between fiber bundles as described below, a thermoplastic resin It can be controlled by the temperature and the like of. On the other hand in the case where the fiber bundle of the organic filaments impregnated with a thermosetting resin to obtain a composite material, because the resin is impregnated thermosetting resin before curing to the inside fiber bundles because of the low viscosity, lowered physical properties, for example impact resistance is lowered.
[Composite]
　The present invention is a composite material having a melting point consists of between 200 ℃ and 500 ℃ organic filaments and the thermoplastic resin. In the present invention, the composition ratio of the organic filaments and the thermoplastic resin, to the organic filaments 100 parts by volume, it is preferred that the thermoplastic resin is 900 parts 20 parts, more preferably 400 parts to 25 parts of it is. If the proportion of the thermoplastic resin to 100 parts of organic filaments is less than 20 parts, between fiber bundles of long fibers have mechanical strength of the composite material becomes covered with voids is greatly reduced. On the contrary, the effect of reinforcing organic fiber length is not sufficiently exhibited and is more than 900 parts.
　Basis weight of the organic filaments per thickness 10mm in the composite material, 1000 ~ 12000 g / yd 2 is preferably. More preferably ～ 10000G 2000 / M 2 is. The organic filament basis weight is 1000 g / yd of 2 smaller than the required energy absorption performance is hardly expressed. Conversely, 12000 g / yd 2 voids tends to occur between the fiber bundle larger the long fibers from, there is a possibility that mechanical strength of the composite material is greatly reduced.
[Thermoplastic Resin]
　composite material of the present invention, high strength along with impact resistance, since it aims at both a high elasticity, it is preferred that the matrix is generally a thermoplastic resin, thermoplastic elastomer or rubber such as elastic material is not suitable. As the rule of thumb, it is preferable that the thermal deformation temperature of the matrix is 80 ℃ or more. As an indicator of thermal deformation of using a deflection temperature under load.
　The thermoplastic resin constituting the composite material of the present invention, for example, vinyl chloride resins, vinylidene chloride resins, vinyl acetate resins, polyvinyl alcohol resins, polystyrene resins, acrylonitrile - styrene resins (AS resins), acrylonitrile - butadiene - styrene resin ( ABS resin), acrylic resin, methacrylic resin, polyethylene resin, polypropylene resin, polyamide 6 resin, a polyamide 11 resin, a polyamide 12 resin, a polyamide 46 resin, a polyamide 66 resin, a polyamide 610 resin, polyacetal resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyethylene-butylene terephthalate resin, polyarylate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resins, polyether ether ketone resins.
　Among these, vinyl chloride resins, polystyrene resins, ABS resin, polyethylene resin, polypropylene resin, polyamide 6 resin, a polyamide 66 resin, polyacetal resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyethylene-butylene terephthalate resin, polyarylate resin is more preferable, and particularly preferred are polypropylene resins, polyethylene terephthalate resins, polycarbonate resins, polyamide 6 resin, a polyamide 66 resin.
[Production Method]
　composite material of the present invention, as well as the method for producing a molded article comprising the composite material, composed of shaping the composite, and the resulting composite material by impregnation of the resin into between fiber bundles. Impregnation of resin into between fiber bundles is not particularly limited, as appropriate depending on the form of the organic filaments to be used, it may be selected. For example, when the organic filaments of the fabric form such as woven or knitted fabric, by using a press molding machine or vacuum molding machine, a thermoplastic resin is melted, at a temperature at which the organic fibers are not melt, laminated fabrics, knitted and the resin the film, nonwoven fabric by elevated or reduced pressure, it is possible to obtain a composite material thermoplastic resin is impregnated between the long-fiber bundle. Further, when the organic filaments are twisted yarn cord, in addition to the above press molding or vacuum molding, it is possible to obtain a composite material that the thermoplastic resin is impregnated between even long-fiber bundle by extrusion molding or pultrusion. For example, while feeding a plurality of twisted yarn code tailored to the creel stand under a constant tension, aligned drawn using the yarn guide, it is introduced into the impregnation die of pultrusion machine. Here, after the molten resin is impregnated between the twisting code, by cooling pull out from the impregnation die, it is possible to obtain a UD sheet of continuous fibers.
　No particular limitation is imposed on the shaping method may be conducted simultaneously with impregnation of the resin into the inter-fiber bundles may be again shaped to after once impregnated with a resin to between fiber bundles. When performing resin impregnation and shaping at the same time, it is possible to easily obtain a shaped body by utilizing a mold desired shape can be obtained. Even when performed separately resin-impregnated and shaped, it can be relatively easily shaped by utilizing the like mold of a desired shape.
　By devising this way the shaping method, it can be made ​​from a large, flat, thin member to the small size and complex shape member. The shape of the molded body, corrugated, truss, three-dimensional form, such as a honeycomb, and the like in addition to the flat plate.
　Organic long fiber bundles and between the resin impregnation of the control of the fiber bundle inside the above twisted yarn, fabrics, in addition to the type selection of the knitted fabric structure and thermoplastic resin, appropriately adjusted in molding conditions. In general, if Takamere the molding temperature and pressure, the resins of the permeability is increased in order to melt viscosity of the resin is reduced. Temperature, the resin melting point + 50 ℃ melting point temperature in the case of a crystalline resin, the range from the glass transition temperature of the melting point + 50 ℃ in the case of the resin is amorphous resin is preferred. Pressure in the range of 20MPa from 0.01 MPa, time is preferably in the range of about 1 hour 30 seconds.
　The combination of the organic filaments and the thermoplastic resin, when the resin used is a crystalline resin, the melting point of the fibers is preferably greater 10 ° C. or higher than the melting point of the resin. Further, when the resin to be used is amorphous resin, the melting point of the fibers is preferably greater 10 ° C. or higher than the glass transition temperature of the resin. In this respect, the organic filaments is a polyester filament or nylon filaments, the thermoplastic resin is polypropylene resin, polyethylene terephthalate resin, polycarbonate resin, polyamide 6 resin, or a combination of a polyamide 66 resin is preferred. More specifically, when the organic filaments are nylon 6 filament is thermoplastic resin is preferably a combination of a polypropylene resin, if the organic filaments is polyethylene terephthalate fiber or a nylon 66 filament, the thermal可塑性樹脂はポリプロピレン樹脂、ポリカーボネート樹脂、ポリアミド６樹脂が好ましい。

Example
[0008]
　The following examples further illustrate the present invention. The present invention is not intended to be anything like limited thereto.
1) The number of twist of the organic fiber measurement
　woven, knitted fabric, the configuration yarn from twisting code samples, was measured the number of twist per 1m a (T / m). Configuration thread to measure the number of the twist in the case of single-stranded (one more), twist the top in the case of plied (2-strand), to measure the number of twist of each twisted below.
2) fiber (organic long fiber and reinforcing fiber) / fiber volume fraction measurement of resin
　1Cm 2 from 10Cm 2 weighing the weight of the sample. Dissolution either of fiber or resin, or by using the decomposing chemicals to extract the dissolved components. The residue is weighed after washing and drying. The weight of the residue and dissolved components, and fiber and resin from specific gravity, to calculate the volume fraction of fiber and resin. For example, if the resin is a polypropylene, the use of heated toluene or xylene, can be dissolved polypropylene only. If the resin is a polyamide, it is possible to decompose a polyamide by heating with formic acid. The use of heated chlorinated hydrocarbons when the resin is a polycarbonate, it is possible to dissolve the polycarbonate. Also from the fiber volume fraction of the fiber / resin, relative to 100 parts of fibers, when the volume of the resin can be obtained, for example, fiber volume fraction is 50%, 100 parts of resin with respect to the volume portion of the fiber 100 It becomes a part.
3) fibers basis weight rating per composites 10mm thick
　fiber volume fraction in the composite, and a fiber density per composites 10mm thick fiber basis weight (g / yd 2 was calculated).
4) void fraction measurements between fiber bundle
　samples were cut with a microtome, to calculate the void fraction by binarizing processing between the fiber bundles its cross-section and microscopic observation.
5) impregnating Evaluation of resin into the fiber
　for high rigidity material, a sample of cross-section and microscopic observation to evaluate the impregnation of the resin by calculating the ratio of the bubble. For composites, loosen the long fibers taken out from the sample using tweezers or a needle, from readily multifilament construction the number of single yarns which can be selected, to calculate the free single yarn rate. For example, in the case of organic long fiber consists of a single yarn of 250 lines, free single yarn rate If you take out a free single yarn of 150 pieces is next to 60%, the impregnation of the resin and the remaining 40% in volume fraction the fact that.
6) Tensile test
　Tensile test of the high-rigidity material and the sandwich material, by reference to JIS K 7165, was measured using the A & D Co. Tensilon universal testing machine. The shape of the test piece was set to A type test pieces, width 15 mm, a thickness was set to 2 mm. Chuck distance is 136mm, the test speed was 2mm / min. For composite material, in compliance with JIS K 7113, it was measured using an autograph AG-the I type manufactured by Shimadzu Corporation. The shape of the test piece was set to No. 1 form test piece, the length of the sample length portion 60 mm, width was 10 mm. Chuck distance is 115mm, the test speed was 10mm / min.
7) falling weight impact test of the molded article
　was measured using an Instron Corp. Dynatup falling weight impact tester 9250HV type. Test specimen size 150mm × 100mm, weight weight 5.43kg, was a load amount of energy 45J.
8) High-speed punching test
　manufactured by Shimadzu Corporation of hydro-shot HITS-P10 type, was ISO 6603-2 maximum load and the absorption amount of energy at the time of punching a test piece in compliance with the standard, and the maximum load point displacement measured. Test specimen size and 140mm × 140mm, the striker diameter of 10mm, the opening size of the holding jig is 40mm, the test speed was 11m / sec. Displacement obtained in this test - and the area of the load curve was evaluated as the absorption of energy loss of the specimen.
9) compression test
　using the A & D Co. Tensilon universal testing machine, was determined according to SACMA SRM1 standards. The shape of the test piece width rectangular 15 mm, length 80 mm, gauge length was set to 4.8 mm. Test speed was 1 mm / min.
[Raw materials
used] 1) polypropylene film
　Saint-Tox Inc. San Tox -CP film, K grade, thickness 30Myuemu
2) polyamide 6 film
　, manufactured by Unitika Ltd. emblem ON film, standard grade, thickness 25Myuemu
3) polycarbonate film
　Teijin Kasei Co., Ltd. bread film produced by using the light L-1225L, thickness 100Myuemu
4) polyethylene terephthalate film
　Teijin DuPont films Teijin Tetron film, standard S grade, thickness 25Myuemu
5) polyethylene terephthalate film
　Teijin DuPont films Teijin Teonex film, standard Q51 grade, thickness 25Myuemu
6) polyethylene terephthalate textile
　Teijin fiber Co., Ltd. T-4498 fabric: Yarn; polyethylene terephthalate fiber 1100dtex192f, twist number; 120T / m (S direction), tissue; plain weave, thickness; 0.4mm, weight per unit area; 175g / m 2
7) polyethylene naphthalate textile
　Teijin fiber Co., Ltd. PF-1200 fabric: Yarn; polyethylene naphthalate fiber 1100dtex250f (less than the melting point 280 ℃), the number of twist; 30T / m (S direction), tissue; twill, thickness; 0 .5mm, weight per unit area; 310G / M
2 8) polyethylene terephthalate knitting
　Teijin fiber manufactured by T-11588 fabric: Yarn; polyethylene terephthalate fiber 560dtex96f, the number of twist; 60T / m (S direction), tissue; Russell knitting, thickness; 0 .3mm, weight per unit area; 120G / M
2 9) polyethylene terephthalate twisted yarn code
　Teijin fiber manufactured by polyethylene terephthalate fiber P900M 1100T250f the original yarn, multiplied by the twisted under the 275T / m in the Z direction using the Kaji Technology Corporation Ltd. of ring twisting machine It was (twist coefficient 3.0). Then, move the lower twisting two, over a twist on the 200T / m in S direction (twist coefficient 3.0), was a twisting code for the experiment. Twisting code one diameter was 0.5 mm. In addition to this twist number up / down in a similar manner: 7/10 (T / m), 710/1000 (T / m), to obtain a twisted yarn cord of 965/1365 (T / m) .
10) polyethylene naphthalate twisting code A
　Teijin fiber manufactured by polyethylene naphthalate fiber Q904M 1100T250f (melting point: 280 less than ℃) and raw yarn, subjected to the same processing and polyethylene terephthalate twisted yarn code, the number of twist up / down: 200/275 ( to obtain a T / m) twisting code.
11) polyethylene naphthalate twisting code
　B as WO2009 / 113555 raw yarn polyethylene naphthalate fiber 1100dtex250f of equal to or higher than the melting point 285 ℃, which was reeling by the method described in Japanese, the same processing and polyethylene terephthalate twisted yarn code, up / down twist number: got a twisted yarn code of 200/275 (T / m).
12) nylon 66 twisting code
　Asahi Kasei Fibers Corp. nylon 66 fiber T5 940T140f the original yarn, subjected to the same processing and polyethylene terephthalate twisted yarn code, the number of twist up / down: to obtain a twisted yarn code of 210/300 (T / m) It was.
13) polyethylene terephthalate non-twist yarns code
　Teijin fiber manufactured by polyethylene terephthalate fiber P900M 1100T250f the original yarn, those two Hongo yarn without adding a twist to the non-twist yarns code.
14) polyethylene terephthalate staple fibers
　Teijin fiber manufactured by polyethylene terephthalate fiber P900M 1100T250f the original yarn, was cut to a length of 1mm using a guillotine cutter.
15) carbon fiber yarn
　Toho Tenax Co., Ltd. STS40 24K (fineness 16000dtex), and HTS40 was using the 12K (fineness 8000dtex). Specific modulus 12.2
16) carbon fibers short fibers
　cut into 5-50mm length using a rotary cutter carbon fiber yarn.
17) carbon fiber woven fabric
　was woven using the Toho Tenax Co., Ltd. STS40 rapier loom 24K. Weave is a plain weave, basis weight 200G / M 2 was adjusted to.
18) glass fiber yarn
　Nitto Boseki Co., Ltd. RS240 QR-483 ratio elastic
4.2 19) aramid fiber
　manufactured by Teijin Techno Products, Inc. TECHNORA T-241J 1670T1000f. In the experiment, the raw yarn and doubling while aligning ten argument was used to adjust the fineness to 16700dtex. Specific elastic 5.1
Example 1: polyethylene naphthalate fabric / polypropylene molded
　polyethylene naphthalate fabrics and polypropylene film, film 8 sheets / fabric 1 sheets / film 16 sheets / fabric 1 sheets / film 16 sheets / fabric one / film 16 sheets / fabric 1 sheets / film 8 sheets of laminated in order, using a Meiki made ​​hot press MHPC type, a maximum temperature of 200 ℃, the polypropylene film by heating and pressurizing for 10 minutes at a maximum pressure 0.5MPa molten, impregnated with polypropylene between the fiber bundles of polyethylene naphthalate fabrics. Thereafter, the mixture was cooled with pressurized state, to obtain a molded body of a polyethylene naphthalate fabric / polypropylene. The thickness of the molded product is 1.6 mm, the volume fraction of the fabric was 35%. Impregnation of the polypropylene into the fiber bundle was 35% by volume fraction. From the resulting molded article, based on the warp direction of the fabric was evaluated by cutting out a tensile test piece. Further, the falling weight impact test pieces were evaluated by cutting out high-speed punching test piece. The evaluation results are shown in Table 1.
Example 2: Polyethylene terephthalate textile / polypropylene molded
　polyethylene terephthalate fabrics and polypropylene film, film 4 sheets / fabric 1 sheets / film 8 sheets / fabric 1 sheets / film 8 sheets / fabric 1 sheets / film 8 sheets / fabric one / except that the laminated film to four forward performs the same processing as in example 1, to obtain a molded body of a polyethylene terephthalate woven fabric / polypropylene. The thickness of the molded product is 1.4 mm, the volume fraction of the fabric was 37%. Impregnation of the polypropylene into the fiber bundle was 30% by volume fraction. The evaluation results are shown in Table 1.
Example 3: Polyethylene terephthalate fabric / polypropylene molded article
　molding conditions 210 ° C., except that the 2.0MPa performs the same processing as in Example 2 to obtain a molded body of a polyethylene terephthalate woven fabric / polypropylene. The thickness of the molded product is 1.3 mm, the volume fraction of the fabric was 37%. Impregnation of the polypropylene into the fiber bundle was 95% by volume fraction. The evaluation results are shown in Table 1.
Example 4: polyethylene terephthalate knitted fabric / polypropylene molded
　polyethylene terephthalate knitted fabric and polypropylene film, film 3 sheets / knit 1 sheets / film 6 sheets / knit 1 sheets / film 6 sheets / knit 1 sheets / film 6 sheets / knit one / except that laminated to the film three forward performs the same processing as in example 1 to obtain an integral molding of polyethylene terephthalate knitted / polypropylene. The thickness of the molded product is 0.9 mm, the volume fraction of the knitted fabric was 34%. Impregnation of the polypropylene into the fiber was 28% by volume fraction. The evaluation results are shown in Table 1.
Example 5: polyethylene terephthalate twisted thread code / polypropylene molded
　after sticking a polypropylene film six in an aluminum plate, the number of twist up / down on this: 200/275 polyethylene terephthalate twisted yarn code of (T / m) 100g under tension, wound at a pitch of 1mm. Then, polypropylene film by this after you paste the six film on top of the twisting code, using a Meiki made ​​hot press MHPC type, a maximum temperature of 200 ℃, heating and pressing for 10 minutes at a maximum pressure 0.5MPa It was melted, impregnated polypropylene between the code of polyethylene terephthalate twisted yarn code. Thereafter, the mixture was cooled with pressurized state, to obtain a polyethylene terephthalate twisted yarn cord / polypropylene integrally molded body. The thickness of the molded product is 0.4 mm, the volume fraction of the twisted yarn cord was 33%. Impregnation of the polypropylene into the fiber was 15% by volume fraction. From the resulting molded article, based on the twisted yarn cord direction it was evaluated by cutting a tensile test piece. Further, to obtain a molded body twisting code 0 degree direction, 90 ° direction, again heated and pressurized after overlapped with the 0 degree direction, the 3-ply molding of polyethylene terephthalate twisted yarn cord / polypropylene by cooling thereafter pressurized state It was. The thickness of the molded product is 1.2 mm, the volume fraction of the twisted yarn cord was 33%. It was evaluated by cutting a falling weight impact test piece and a high-speed stamping specimens from the 3-ply molded body. The evaluation results are shown in Table 1.
Example 6: Polyethylene terephthalate twisted yarn cord / polypropylene molded article
　molding conditions 210 ° C., except that the 2.0MPa performs the same processing as in Example 5, to obtain a polyethylene terephthalate twisted yarn cord / polypropylene integrally molded body. The thickness of the molded product is 0.4 mm, the volume fraction of the twisted yarn cord was 33%. Impregnation of the polypropylene to the fiber was 70% in the volume fraction. The evaluation results are shown in Table 1.
Comparative Example 1: polyethylene terephthalate short fiber / polypropylene molded
the cut length of 1mm polyethylene terephthalate staple fibers and polypropylene resin, and kneaded for 1 minute at 210 ℃ by using the Thermo Plastics Industry Co., Ltd. of the single-screw extruder TP15 type, polyethylene terephthalate to obtain a composite material strands of staple fibers and polypropylene. Then, using a small injection molding machine EP5 type manufactured by Nissei Plastic Industrial Co., the obtained strands, specimens with 210 ° C., falling weight impact test pieces were prepared fast punching test piece. The volume fraction of fibers in the specimen increased to 34%. Sectional result of laser microscope observation of the specimen, the short fibers are dispersed well in resin divided up into single yarn level, aggregates of single yarns was observed (impregnation of the polypropylene at a volume fraction 100%). The evaluation results are shown in Table 1.
Comparative Example 2: polypropylene molded
　the 40 sheets of polypropylene film was laminated, using a Meiki made ​​hot press MHPC type, a maximum temperature of 200 ℃, the polypropylene film is melted by heating and pressurizing for 10 minutes at a maximum pressure 1.0MPa , then, to obtain a molded article of polypropylene by cooling with pressurized condition. The thickness of the shaped body was 1.2 mm. The evaluation results are shown in Table 1.
Comparative Example 3: polycarbonate molded
　twelve polycarbonate film was laminated, using a Meiki made ​​hot press MHPC type, a maximum temperature of 250 ℃, softening and melting the polycarbonate film by heating and pressurizing for 10 minutes at a maximum pressure 2.0MPa and, thereafter, to obtain a molded body of a polycarbonate by cooling with pressurized condition. The thickness of the shaped body was 1.2 mm. The evaluation results are shown in Table 2.
Example 7: polyethylene terephthalate twisted thread code / polyamide 6 molded
　after pasting a polyamide 6 film seven in an aluminum plate, the number of twist up / down on this: 200/275 polyethylene terephthalate twisted yarn code of (T / m) the tension under 100 g, wound at a pitch of 1 mm. Then, polyamide by after pasting the seven films on this twisting code, using a Meiki made ​​hot press MHPC type, a maximum temperature of 240 ℃, heating and pressing for 10 minutes at a maximum pressure 0.5MPa 6 film was melted, impregnated with polyamide 6 between the code of polyethylene terephthalate twisted yarn code. Thereafter, the mixture was cooled with pressurized state, to obtain a polyethylene terephthalate twisted yarn cord / polyamide 6 integrally molded body. The thickness of the molded product is 0.4 mm, the volume fraction of the twisted yarn cord was 35%. Impregnation of the polyamide 6 into the fiber was 20% by volume fraction. From the resulting molded article, based on the twisted yarn cord direction it was evaluated by cutting a tensile test piece. Further, the compact twine code 0 degree direction, 90 ° direction, again heated and pressurized after overlapped with the 0 degree direction, the 3-ply molding of polyethylene terephthalate twisted yarn cord / polyamide 6 by cooling thereafter pressurized state Obtained. The thickness of the molded product is 1.2 mm, the volume fraction of the twisted yarn cord was 35%. It was evaluated by cutting a falling weight impact test piece and a high-speed stamping specimens from the 3-ply molded body. The evaluation results are shown in Table 2.
Example 8: polyethylene terephthalate twisted thread code / polycarbonate molded body
　after attaching the two polycarbonate film in an aluminum plate, the number of twist up / down on this: 200/275 polyethylene terephthalate twisted yarn code of (T / m) certain under tension, wound at a pitch of about 1mm. Next, a polycarbonate film by this after you paste the two films on the twisting code, using a Meiki made ​​hot press MHPC type, a maximum temperature of 250 ℃, heating and pressing for 10 minutes at a maximum pressure 2.0MPa softened melted, impregnated with polycarbonate between the code of polyethylene terephthalate twisted yarn code. Thereafter, the mixture was cooled with pressurized state, to obtain a polyethylene terephthalate twisted yarn cord / polycarbonate molded body. The thickness of the molded product is 0.4 mm, the volume fraction of the twisted yarn cord was 30%. Impregnation of the polycarbonate into the fiber was 10% by volume fraction. From the resulting molded article, based on the twisted yarn cord direction it was evaluated by cutting a tensile test piece. Further, to obtain a molded body twisting code 0 degree direction, 90 ° direction, again heated and pressurized after overlapped with the 0 degree direction, the 3-ply molding of polyethylene terephthalate twisted yarn cord / polycarbonate by cooling thereafter pressurized state It was. The thickness of the molded product is 1.3 mm, the volume fraction of the twisted yarn cord was 30%. It was evaluated by cutting a falling weight impact test piece and a high-speed stamping specimens from the 3-ply molded body. The evaluation results are shown in Table 2.
Example 9: polyethylene naphthalate woven / polyethylene terephthalate molded
　polyethylene naphthalate fabric and polyethylene terephthalate film, the film 10 sheets / fabric 1 sheets / film 19 sheets / fabric 1 sheets / film 19 sheets / fabric 1 sheets / film 19 sheets / textile 1 sheets / film 10 sheets of laminated in order, using a Meiki made ​​hot press MHPC type, a maximum temperature of 270 ℃, melting the polyethylene terephthalate film by heating and pressurizing for 10 minutes at a maximum pressure 2.0MPa, impregnated with polyethylene terephthalate between the fiber bundles of polyethylene naphthalate fabric. Thereafter, the mixture was cooled with pressurized state, to obtain a molded body of a polyethylene naphthalate woven / polyethylene terephthalate. The thickness of the molded product is 1.6 mm, the volume fraction of the fabric was 35%. Impregnation of the polyethylene terephthalate into the fiber was 23% by volume fraction. The evaluation results are shown in Table 2.
Comparative Example 4: polyamide 6 molded
　50 sheets polyamide 6 film was laminated, using a Meiki made ​​hot press MHPC type, polyamide 6 film by a maximum temperature of 240 ℃, heating and pressing for 10 minutes at a maximum pressure 2.0MPa melted, then to obtain a molded article of polyamide 6 by cooling with pressurized condition. The thickness of the shaped body was 1.2 mm. These results are shown in Table 2.
Comparative Example 5: Polyethylene terephthalate molded article
　by laminating 50 sheets of polyethylene terephthalate, using a Meiki made ​​hot press MHPC type, maximum temperature 270 ° C., molten polyethylene terephthalate by heating and pressurizing for 10 minutes at maximum pressure 2.0MPa and, thereafter, to obtain a molded article of polyethylene terephthalate by cooling with pressurized condition. The thickness of the shaped body was 1.2 mm. The evaluation results are shown in Table 2.
Examples 10-28
　types of fibers, the form, the various polypropylene-based composite material by a number or the like twisted changed to those shown in Table 3 or 4, the press treatment at the molding conditions shown in Examples 1-6 Preparation ,evaluated. Table 3 The evaluation results are shown in Table 4.
Example 29: polyethylene terephthalate twisted thread code / polyamide 6 molded
　after pasting a polyamide 6 film three in an aluminum plate, the number of twist up / down on this: 200/275 polyethylene terephthalate twisted yarn code of (T / m) the tension under 100 g, wound at a pitch of 2 mm. Then, polyamide by after pasting the four films on this twisting code, using a Meiki made ​​hot press MHPC type, a maximum temperature of 240 ℃, heating and pressing for 10 minutes at a maximum pressure 2.0MPa 6 film was melted, impregnated with polyamide 6 between the code of polyethylene terephthalate twisted yarn code. Thereafter, the mixture was cooled with pressurized state, to obtain a polyethylene terephthalate twisted yarn cord / polyamide 6 integrally molded body. The thickness of the molded product is 0.3 mm, the volume fraction of the twisted yarn cord was 35%. Impregnation of the polyamide 6 into the fiber was 56% by volume fraction. From the resulting molded article, based on the twisted yarn cord direction it was evaluated by cutting a tensile test piece. Further, the compact twine code 0 degree direction, 90 ° direction, again heated and pressurized after overlapped with the 0 degree direction, the 3-ply molding of polyethylene terephthalate twisted yarn cord / polyamide 6 by cooling thereafter pressurized state Obtained. The thickness of the molded product is 0.9 mm, the volume fraction of the twisted yarn cord was 35%. It was evaluated by cutting a falling weight impact test piece and a high-speed stamping specimens from the 3-ply molded body. The evaluation results are shown in Table 4.
Examples 30-40
　types of fibers, the form, changing the number or twisted to those shown in Table 5 or 6, various nylon 6 based composite material by pressing at the molding conditions shown in Example 7 or 29 prepared, and evaluated. Table 5. The evaluation results are shown in Table 6.
Example 41: polyethylene terephthalate twisted thread code / polycarbonate molded body
　after pasting a single polycarbonate film in an aluminum plate, the number of twist up / down on this: 200/275 polyethylene terephthalate twisted yarn code of (T / m) certain under tension, wound at a pitch of about 2mm. Next, a polycarbonate film by this after you paste a single film on the twisting code, using a Meiki made ​​hot press MHPC type, a maximum temperature of 250 ℃, heating and pressing for 10 minutes at a maximum pressure 5.0MPa softened melted, impregnated with polycarbonate between the code of polyethylene terephthalate twisted yarn code. Thereafter, the mixture was cooled with pressurized state, to obtain a polyethylene terephthalate twisted yarn cord / polycarbonate molded body. The thickness of the molded product is 0.3 mm, the volume fraction of the twisted yarn cord was 29%. Impregnation of the polycarbonate into the fiber was 48% by volume fraction. From the resulting molded article, based on the twisted yarn cord direction it was evaluated by cutting a tensile test piece. Further, to obtain a molded body twisting code 0 degree direction, 90 ° direction, again heated and pressurized after overlapped with the 0 degree direction, the 3-ply molding of polyethylene terephthalate twisted yarn cord / polycarbonate by cooling thereafter pressurized state It was. The thickness of the molded product is 0.9 mm, the volume fraction of the twisted yarn cord was 29%. It was evaluated by cutting a falling weight impact test piece and a high-speed stamping specimens from the 3-ply molded body. The evaluation results are shown in Table 6.
Examples 42-48
　types of fibers, the form, changing the number or twisted to those shown in Table 6, produce a variety of polycarbonate-based composite material by pressing at the molding conditions shown in Example 8 or 41, evaluation did. The evaluation results are shown in Table 6.
Example 49: polyethylene naphthalate twisting code A / polyethylene terephthalate molded
　after pasting the three polyethylene terephthalate film in an aluminum plate, the number of twist up / down on this: polyethylene Na of 200/275 (T / m) tension under the phthalate twisting code a 100g, wound at a pitch of 1mm. Next, after attaching the four films onto the twisted yarn cord, using a Meiki made ​​hot press MHPC type, maximum temperature 270 ° C., a polyethylene terephthalate by heating and pressurizing for 10 minutes at maximum pressure 3.0MPa film was melted, impregnated with polyethylene terephthalate between the fiber bundles of polyethylene naphthalate twisting code the a. Thereafter, the mixture was cooled with pressurized state, to obtain a molded body of a polyethylene naphthalate twisting code A / polyethylene terephthalate. The thickness of the molded product is 0.3 mm, the volume fraction of the twisted yarn cord was 49%. Impregnation of the polyethylene terephthalate into the fiber was 57% by volume fraction. From the resulting molded article, based on the twisted yarn cord direction it was evaluated by cutting a tensile test piece. Further, the compact twine code 0 degree direction, 90 ° direction, again heated and pressurized after overlapped with the 0 degree direction, 3-ply molding of polyethylene naphthalate twisting code A / polyethylene terephthalate by cooling thereafter pressurized state to give the body. The thickness of the molded product is 1.0 mm, the volume fraction of the twisted yarn cord was 49%. It was evaluated by cutting a falling weight impact test piece and a high-speed stamping specimens from the 3-ply molded body. The evaluation results are shown in Table 6.
Example 50: polyethylene naphthalate woven / polyethylene terephthalate molded
　polyethylene naphthalate fabric and polyethylene terephthalate film, film five / fabrics 1 sheets / film 10 sheets / fabric 1 sheets / film 10 sheets / fabric 1 sheets / film 10 sheets / textile 1 sheets / film five stacked in this order, using a Meiki made ​​hot press MHPC type, a maximum temperature of 270 ℃, melting the polyethylene terephthalate film by heating and pressurizing for 10 minutes at a maximum pressure 3.0MPa, impregnated with polyethylene terephthalate between the fiber bundles of polyethylene naphthalate fabric. The thickness was 1.0 mm. The thickness was 1.0 mm. The thickness was 1.0 mm. 　The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. 　The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. 　The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. 　The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. 　From the resulting two-directional high rigidity material was evaluated by cutting out a tensile test specimens and the compression test piece one of the fiber axis direction as a reference. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece. 　The thickness was 1.0 mm. The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. 　Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece. 　It had a thickness of 0.5mm. The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. 　The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. 　The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. 　The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. 　The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. 　The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. The evaluation results are shown in Table 16. 　From the resulting two-directional high rigidity material was evaluated by cutting out a tensile test specimens and the compression test piece one of the fiber axis direction as a reference. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece. The evaluation results are shown in Table 16. 　Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece. The evaluation results are shown in Table 16. 　The thickness was 1.0 mm. The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. The evaluation results are shown in Table 16.

　Charged into a mold of 30cm × 20cm polypropylene film by laminating 19 sheets, using a Meiki made ​​hot press MHPC type, a maximum temperature of 200 ℃, by heating and pressurizing for 10 minutes at a maximum pressure 0.5MPa, of polypropylene to obtain a molded product. It had a thickness of 0.5mm. The resulting polypropylene molded article as the skin material, was charged with one sandwiching a core material of polyethylene terephthalate twisted yarn cord / polypropylene resin composite material of Example 56 in a mold of 30 cm × 20 cm, a Meiki made ​​hot press MHPC type used, maximum temperature of 200 ℃, and welding the interface between the skin material and the core material by heating and pressurizing for 10 minutes at a maximum pressure 0.2MPa, got a sandwich material of polypropylene resin / polyethylene terephthalate twisted yarn code. The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. From the obtained sandwich material was evaluated by cutting test pieces and compression specimens tensile fiber axis direction as a reference. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. The evaluation results are shown in Table 16.
Example 70: Glass fiber length fiber / polyethylene terephthalate twisted thread code / polyamide 6 resin sandwich material made ​​of
　except that the reference example 7 glass fiber length of fiber / polyamide 6 resin and high stiffness material of the skin material, the same manner as in Example 57 It performs a process to obtain a sandwich material of the glass fiber filaments / polyethylene terephthalate twisted yarn cord / polyamide 6 resin. The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. From the obtained sandwich material was evaluated by cutting test pieces and compression test piece Tensile glass fiber direction as a reference. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. The evaluation results are shown in Table 17.
Comparative Example 14: Glass fiber length fiber / polyamide 6 resin bi-directional high-rigidity material made ​​of
　a glass fiber length of fiber / polyamide 6 resin and high rigidity material of Reference Example 7, the 0-degree direction of the fiber axis direction as a standard, 90-degree direction , 90-degree direction, stacked four in the 0-degree direction was charged in a mold of 30cm × 20cm, using the Meiki made ​​hot press MHPC type, a maximum temperature of 240 ℃, heat and pressure for 10 minutes at a maximum pressure 0.5MPa by welding interface of each layer by applying, to obtain a bi-directional high rigidity material of the glass fiber filaments / polyamide 6 resin. The thickness of the high rigidity material was 2.0 mm. From the resulting two-directional high rigidity material was evaluated by cutting out a tensile test specimens and the compression test piece one of the fiber axis direction as a reference. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece. The evaluation results are shown in Table 17.
Comparative Example 15: Production of glass fiber length fiber / polyamide 6 resin sandwich material
　polyamide 6 film by stacking 44 sheets were placed in a mold of 30cm × 20cm, using a Meiki made ​​hot press MHPC type, a maximum temperature of 240 ℃ , by heating and pressurizing for 10 minutes at maximum pressure 0.5 MPa, to obtain a molded article of polyamide 6. The thickness was 1.0 mm. The obtained polyamide 6 molded products as a core material, those sandwiched between skin material 2 sheets of glass fiber length fiber / polyamide 6 resin and high rigidity material of Reference Example 7, was charged in a mold of 30cm × 20cm, Meiki by using a manufacturing hot press MHPC type, a maximum temperature of 240 ℃, and welding the interface between the skin material and the core material by heating and pressurizing for 10 minutes at a maximum pressure 0.2MPa, sandwich material of glass fiber length fiber / polyamide 6 resin It was obtained. The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. From the obtained sandwich material was evaluated by cutting test pieces and compression test piece Tensile glass fiber direction as a reference. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. The evaluation results are shown in Table 17.
Example 71: aramid fiber filaments / polyethylene terephthalate twisted yarn cord / Production of Polyamide 6 resin sandwich material
　except that the aramid fiber length of Reference Example 8 fibers / polyamide 6 resin and high rigidity material was changed to the skin material, as in Example 57 It performs a process to obtain a sandwich material of an aramid fiber filaments / polyethylene terephthalate twisted yarn cord / polyamide 6 resin. The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. From the obtained sandwich material was evaluated by cutting test pieces and compression test piece Tensile aramid fiber direction as a reference. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. The evaluation results are shown in Table 17.
Comparative Example 16: aramid fiber length fiber / polyamide 6 resin bi-directional high-rigidity material made ​​of
　aramid fiber length fiber / polyamide 6 resin and high rigidity material of Reference Example 8, the 0-degree direction of the fiber axis direction as a standard, 90-degree direction , 90-degree direction, stacked four in the 0-degree direction was charged in a mold of 30cm × 20cm, using the Meiki made ​​hot press MHPC type, a maximum temperature of 240 ℃, heat and pressure for 10 minutes at a maximum pressure 0.5MPa by welding interface of each layer by applying, to obtain a bi-directional high-rigidity material aramid fiber filaments / polyamide 6 resin. The thickness of the high rigidity material was 2.0 mm. From the resulting two-directional high rigidity material was evaluated by cutting out a tensile test specimens and the compression test piece one of the fiber axis direction as a reference. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece. The evaluation results are shown in Table 17.
Comparative Example 17: Production of aramid fiber length fiber / polyamide 6 resin sandwich material
　polyamide 6 film by stacking 44 sheets were placed in a mold of 30cm × 20cm, using a Meiki made ​​hot press MHPC type, a maximum temperature of 240 ℃ , by heating and pressurizing for 10 minutes at maximum pressure 0.5 MPa, to obtain a molded article of polyamide 6. The thickness was 1.0 mm. The obtained polyamide 6 molded products as a core material, those sandwiched between skin material 2 sheets of aramid fiber length fiber / polyamide 6 resin and high rigidity material of Reference Example 8, was charged into a mold of 30cm × 20cm, Meiki by using a manufacturing hot press MHPC type, a maximum temperature of 240 ℃, and welding the interface between the skin material and the core material by heating and pressurizing for 10 minutes at a maximum pressure 0.2MPa, sandwich material of aramid fiber length fiber / polyamide 6 resin It was obtained. The thickness of the sandwich material 2.0 mm, the volume fraction of the core material was 50%. From the obtained sandwich material was evaluated by cutting test pieces and compression test piece Tensile aramid fiber direction as a reference. Similarly, it was evaluated by cutting also drop weight test piece and a high-speed punching test piece from the sandwich material. The evaluation results are shown in Table 17.
Example 72: Preparation of carbon fiber short fiber / polyethylene terephthalate twisted thread code / polycarbonate resin sandwich material
　of polyethylene terephthalate twisted thread code / polycarbonate resin composite material of Example 42 as a core material, carbon fiber of Reference Example 35 short fiber / polycarbonate resin High what it is sandwiched by the skin material 2 sheets of rigid material, charged into a mold of 30cm × 20cm, using a Meiki made ​​hot press MHPC type, a maximum temperature of 250 ℃, heating and pressing for 10 minutes at a maximum pressure 0.5MPa welded interface skins material and the core material by, to obtain a sandwich material of a carbon fiber short fiber / polyethylene terephthalate twisted yarn cord / polypropylene resin. The thickness of the sandwich material 4.0 mm, the volume fraction of the core material was 50%. From the resulting sandwich material, tensile specimen, a compression test piece, drop weight test pieces were evaluated by cutting a high-speed punching test piece. The evaluation results are shown in Table 18.
Comparative Example 18: Preparation of carbon fiber short fiber / polycarbonate resin sandwich material
　charged into a mold of 30cm × 20cm by stacking 11 sheets of polycarbonate film, using a Meiki made ​​hot press MHPC type, a maximum temperature of 250 ℃, maximum by heating and pressing for 10 minutes at a pressure of 2.0 MPa, to obtain a polycarbonate molded article. The thickness was 1.0 mm. The obtained polycarbonate molded products as a core material, those sandwiched between skin material 2 sheets of carbon fiber short fiber / polycarbonate resin and high rigidity material of Reference Example 35, was charged in a mold of 30cm × 20cm, Meiki made ​​hot using a press MHPC type, a maximum temperature of 250 ℃, and welding the interface between the skin material and the core material by heating and pressurizing for 10 minutes at a maximum pressure 0.5MPa, got a sandwich material of carbon fiber short fiber / polycarbonate resin . The thickness of the sandwich material 4.0 mm, the volume fraction of the core material was 50%. From the resulting sandwich material, tensile specimen, a compression test piece, drop weight test pieces were evaluated by cutting a high-speed punching test piece. The evaluation results are shown in Table 18.
Example 73: carbon fiber short fiber / polyethylene naphthalate twisting code / polyethylene terephthalate resin sandwich material produced
　polyethylene naphthalate twisting code / polyethylene terephthalate resin composite material of Example 49 as a core material, carbon fiber short fiber of Reference Example 37 / what is sandwiched by the skin material 2 sheets of polyethylene terephthalate resin and high rigidity material, charged into a mold of 30cm × 20cm, using a Meiki made ​​hot press MHPC type, a maximum temperature of 270 ℃, at a maximum pressure 0.2MPa It welded the interface between the skin material and the core material by heating and pressurizing for 10 minutes to obtain a sandwich material of carbon fiber short fiber / polyethylene naphthalate twisting code / polyethylene terephthalate resin. The thickness of the sandwich material 4.0 mm, the volume fraction of the core material was 50%. From the resulting sandwich material, tensile specimen, a compression test piece, drop weight test pieces were evaluated by cutting a high-speed punching test piece. The evaluation results are shown in Table 18.
Comparative Example 19: Preparation of carbon fiber short fiber / polyethylene terephthalate resin sandwich material
　charged into a mold of 30cm × 20cm with a polyethylene terephthalate film by laminating 44 sheets, using a Meiki made ​​hot press MHPC type, maximum temperature of 270 ℃ , by heating and pressurizing for 10 minutes at maximum pressure 2.0 MPa, to obtain a molded article of polyethylene terephthalate. The thickness was 1.0 mm. The resulting polyethylene terephthalate molded article as a core material, those sandwiched between skin material 2 sheets of carbon fiber short fiber / polyethylene terephthalate resin and high rigidity material of Reference Example 37, was charged in a mold of 30cm × 20cm, Meiki by using a manufacturing hot press MHPC type, a maximum temperature of 270 ℃, and welding the interface between the skin material and the core material by heating and pressurizing for 10 minutes at a maximum pressure 0.2MPa, sandwich material of carbon fiber short fiber / polyethylene terephthalate resin It was obtained. The thickness of the sandwich material 4.0 mm, the volume fraction of the core material was 50%. From the resulting sandwich material, tensile specimen, a compression test piece, drop weight test pieces were evaluated by cutting a high-speed punching test piece. The evaluation results are shown in Table 18.
Example 74: Preparation of carbon fiber short fiber / high melting point polyethylene naphthalate twisting code / polyethylene naphthalate resin sandwich material
　a high melting point polyethylene naphthalate twisting code / polyethylene naphthalate resin composite material of Example 51 as a core material, reference example 39 things sandwiched by the skin material 2 sheets of carbon fiber short fiber / polyethylene naphthalate resin highly rigid material, charged into a mold of 30cm × 20cm, using a Meiki made ​​hot press MHPC type, maximum temperature of 280 ℃ , welded interface skins material and the core material by heating and pressurizing for 10 minutes at maximum pressure 0.2 MPa, to obtain a sandwich material of a carbon fiber short fiber / high melting point polyethylene naphthalate twisting code / polyethylene naphthalate resin. The thickness of the sandwich material 4.0 mm, the volume fraction of the core material was 50%. From the resulting sandwich material, tensile specimen, a compression test piece, drop weight test pieces were evaluated by cutting a high-speed punching test piece. The evaluation results are shown in Table 18.
Comparative Example 20: Preparation of carbon fiber short fiber / polyethylene naphthalate resin sandwich material
　charged into a mold of 30cm × 20cm by stacking 44 sheets of polyethylene terephthalate film, using a Meiki made ​​hot press MHPC type, maximum temperature 280 ° C., by heating and pressurizing for 10 minutes at maximum pressure 2.0 MPa, to obtain a molded article of polyethylene naphthalate. The thickness was 1.0 mm. The resulting polyethylene naphthalate molded products as a core material, those sandwiched between skin material 2 sheets of carbon fiber short fiber / polyethylene naphthalate resin highly rigid material of Reference Example 39, was charged in a mold of 30cm × 20cm, name by using the machine Seisakusho hot press MHPC type, a maximum temperature of 280 ℃, and welding the interface between the skin material and the core material by heating and pressurizing for 10 minutes at a maximum pressure 0.2MPa, carbon fiber short fiber / polyethylene naphthalate resin to obtain a sandwich material. The thickness of the sandwich material 4.0 mm, the volume fraction of the core material was 50%. From the resulting sandwich material, tensile specimen, a compression test piece, drop weight test pieces were evaluated by cutting a high-speed punching test piece. The evaluation results are shown in Table 18.
High rigidity material of Reference Example, as a result of the tensile test compression test was a material excellent in strength and elastic modulus. Further, the composite material of the embodiment is a shock absorber was a material rich in energy absorbing. Sandwich materials of Examples 57 to 60, 63 ~ 67, 70 ~ 74 which combines these high stiffness material and the composite material combines the advantages of both excellent mechanical strength of strength and stiffness, even further shock resistance was an excellent material. Such sandwich material molded article was molded is useful for industrial materials in general, is particularly useful structural automotive parts, exterior parts, interior parts.
The following shows the evaluation results of the resulting composite material and sandwich material in Tables 1 to 18.
Description of the code
[0009]
　1 punching direction
　2 striker
　3 opening
　the holding jig of 4 test pieces
　5 test pieces
[Table 1]

The scope of the claims
[Claim 1]
　A composite material having a melting point consists of between 200 ℃ and 500 ℃ organic filaments and the thermoplastic resin, composite the form of organic long fibers, characterized in that it is a constructed fabric or a knitted fabric with twisted yarn cord or twine code, material.
[Claim 2]
　Composite material according to claim 1 melting point of the organic filament is 250 ° C. or higher.
[Claim 3]
　Composite material according to claim 1 the organic filaments is multifilament, the fibers Tabakan, characterized in that the substantially thermoplastic resin is impregnated.
[Claim 4]
　The fiber bundle inside the organic filaments, the composite material according to claim 1, wherein the substantially thermoplastic resin is a non-impregnated.
[Claim 5]
　Composite material according to claim 1 volume ratio of the organic filaments and the thermoplastic resin, that for 100 parts of the organic filaments, the thermoplastic resin is characterized by a 900 parts from 20 parts.
[6.]
　Basis weight of the organic filaments per thickness 10mm in the composite is ~ 12000 g 1000 / yd 2 composite material according to claim 1 which is.
[7.]
　Composite material according to claim 1 in which the twist number of twisting code, characterized in that from 10 to 1000 times per 1 m.
[8.]
　Composite material according to claim 1 the organic filament is a polyester filament or nylon filaments.
[9.]
　Composite material according to claim 8, characterized in that polyester filament is a polyalkylene terephthalate and / or polyalkylene naphthalate and 95 mol% or more of the components in the polyester.
[10.]
　Composite material according to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin resins, polyamide resins, polycarbonate resins, and polyester resins.
[11.]
　Test speed 11m / sec, the composite material according to claim 1, wherein the opening diameter 40mm of the test piece holding fixture, the absorbed energy at high speed punching test using 10mm diameter striker is at least 10 J.
[12.]
　The specific elastic defined by the following formula (1) (E) is a high rigidity member made ​​of a fiber-reinforced composite material containing 2.5 or more reinforcing fibers and a skin material, the composite material according to claim 1, wherein the core material sandwich material.
E = M / D / 9.8 ( 1)
where, E is the elastic modulus of the specific modulus, M fibers (MPa), D is the fiber density of (g / cm 3 is).
[13.]
　Reinforcing fibers of a high rigidity material is carbon fiber, the sandwich material according to claim 12 is at least one selected from the group consisting of aramid fibers, and glass fibers.
[14.]
　The volume ratio of the skin material and the core material, to the skin material 100 parts of the sandwich material according to claim 12 core material is 40 to 9900 parts.