molded product, use of the molded product and method for manufacturing the fiber-reinforced composit

专利摘要:
MOLDED PRODUCT CONSTITUTED BY REINFORCED FIBER COMPOSITE MATERIAL. The present invention relates to a light weight molded product having a degree of freedom of form, consisting of a fiber reinforced composite material containing reinforced fibers and a thermoplastic resin. The present invention relates to a molded product being excellent in the isotropy consisting of a fiber reinforced composite material in which the discontinuous reinforced fibers are isotropic in one plane and are bidimensionally oriented in the thermoplastic resin, the reinforced fibers contained in the molded product include a bundle fiber reinforced A consisting of the reinforced fibers of the critical single fiber number defined by formula (1) or more, an index of the fiber reinforced bundle A to the total amount of the reinforced fibers in the molded product is 20% by volume or more and less than than 90% by volume, and the average number N of the reinforced fibers in the reinforced fiber bundle A meets the formula (2): Critical single fiber number = 600 / D (1) 0.7x104 / D2 1x105 / D2 (2) in that D is an average fiber diameter (μm) of the reinforced fibers.
公开号:BR112013021878B1
申请号:R112013021878-9
申请日:2011-08-31
公开日:2020-12-01
发明作者:Yutaka Yagi；Toru Sugiyama；Yutaka Kondo；Michiharu Taniguchi；Yuhei Konagai；Ikkou Furukawa
申请人:Teijin Limited；
IPC主号:

专利说明:

Technical field
[0001] The present invention relates to a lightweight molded product having a degree of freedom in shape, consisting of fiber-reinforced composite material containing reinforcement fibers and a thermoplastic resin. The invention also relates to a molded product preferably for use in housings for electronic and electrical equipment, parts for automobiles, parts for medical equipment, parts for aircraft, construction materials and parts for general industries. The invention also relates to a method for manufacturing the molded product at high productivity. Background of the Technique
[0002] In recent years, demand for light weight has increased in various fields, such as electrical and electronic equipment, automobiles, medical equipment, aircraft, building materials and parts for general industries and accommodation, and members are required used in these have light weight and high rigidity. A molded product obtained by pressing an aluminum or magnesium alloy sheet, or a molded product obtained by melting it, is used as such housings and high-rigidity end members. In addition, a molded product obtained by injection molding a fiber-reinforced composite material in which the glass fibers or carbon fibers are filled here and a product format obtained by integrating a sheet of composite material reinforced fiber and a thermoplastic resin by injection mold.
[0003] Aluminum alloy and magnesium alloy are excellent in strength and stiffness, but have a limit on malleability and are therefore difficult to obtain a complicated shape in a single substance. In addition, a metal member (particularly a magnesium alloy) has a problem of low corrosion resistance. The surface of the metal member is corroded by moisture in the air or moisture and salt contained in the user's sweat, leading to a weak appearance. In view of this, Patent Document 1 proposes a method for producing a housing including an application step to apply the entire member consisting of a magnesium alloy with a resin layer and a molding step to integrally mold the member and a part made of resin. This method allows the formation of a complicated shape and the improvement of corrosion resistance. However, the steps become complicated and, in addition, the specific strength of an aluminum alloy, a magnesium alloy and a resin is relatively high compared to iron, but is low compared to the fiber reinforced composite material described here. Therefore, there is a limit to the possible lightness to reach.
[0004] The fiber reinforced composite material is excellent in specific strength and stiffness and, moreover, excellent in corrosion resistance and is therefore widely used in the uses described above. In particular, a molded product obtained by injecting into a mold a composite material of reinforced fiber in which glass fibers or carbon fibers are filled there, is widely used due to the high degree of freedom in shape and high productivity. However, due to the length of the fibers that remained in the molded product being short, the problem still remains in the uses that need high strength and rigidity. However, the fiber-reinforced composite material obtained by injection molding, and a complicated shape were difficult to form with a single substance. Furthermore, because the fiber composite material is produced by depositing a plurality of reinforcement fibers in a fabric form, there was a problem of low productivity. Patent Document 2 proposes a combined molded product in which a resin member is joined to a plate-like member consisting of a sheet containing reinforcement fibers, particularly a continuous fiber at an outer boundary of the plate-like member. This constitution makes it possible to obtain a molded product having a complicated shape. However, because the molded product is produced through a plurality of steps, it is difficult to say that productivity is high. In addition, a fiber reinforced composite material using a continuous fiber is generally obtained by heating and pressurizing a material called prepeg, in which a fiber reinforced base material is previously impregnated with a thermosetting resin, for 2 hours or more using an autoclave. In recent years, the RTM molding method has been proposed including setting up a fiber-reinforced base material, in which the resin is not impregnated in a mold, and then placing a thermosetting resin in the mold, and the molding time has been greatly reduced . However, even when using the RTM molding method, 10 minutes or more is required to shape a part and productivity is not improved.
[0005] For this reason, it focused on a fiber reinforced composite material using a thermoplastic resin as a matrix in place of the thermosetting resin. However, thermoplastic resin generally has a high viscosity compared to thermosetting resin. Therefore, there was a problem in the long time to impregnate a fiber based material and, as a result, the extension time for molding becomes long.
[0006] A technique called thermoplastic molding (TP-SMC) has been proposed as a technique to solve these problems. This technique is a molding method including heating cut fibers previously impregnated with a thermoplastic resin to a melting point or a temperature capable of flowing from the resin, or higher, by introducing the cut fibers into a part of a mold, immediately closing the mold and fluidizing the fibers and resin in the mold, thus obtaining a product format, followed by cooling to form a molded product. This technique allows molding in a short time of about 1 minute using fibers previously impregnated with a resin. Patent Documents 3 and 4 describe a method for producing bundles of cut fibers and molding materials. These methods are methods using impression materials such as the so-called SMC or stampable sheet. In such molding by thermoplastic stamping, fibers and resin are allowed to flow into the mold, such that there were problems with failure in the production of a thin wall and the orientation of the fibers is disrupted, making it difficult to control.
[0007] Patent Document 1: JP-A-2010-147376
[0008] Patent Document 2: JP-A-2010-131804
[0009] Patent Document 3: JP-A-2009-114611
[00010] Patent Document 4: JP-A-2009-114612 Description of the Invention Problems to be solved by the invention
[00011] The problem to be solved in the present invention is the supply of a molded product in high productivity, being the molded product of thin wall and light weight, having high rigidity and excellent surface appearance, and having a complicated three-dimensional shape. Means to Solve Problems
[00012] As a result of intensive investigations to solve the above problems, the current inventors have obtained the present invention. That is, the present invention relates to a molded product consisting of a reinforced fiber composite material containing discontinuous reinforcement fibers in a thermoplastic resin, where the reinforcement fibers contained in the molded product have bundles of reinforcement fibers. reinforcement fibers of the critical number of single fiber or more defined by the following formula (1), the ratio of this to the total amount of reinforcement fibers in the molded product is 20% vol or more, and less than 90% vol , and the average number N of the reinforcement fibers in the bundle of reinforcement fibers A satisfies the following formula (2): critical single fiber number = 600 / D (1) 0.7x104 / D2 <N <1x105 / D2 (2 ) where D is the average fiber diameter (μm) of the reinforcement fibers. Advantage of the invention
[00013] According to the present invention, a thin-walled, light-weight molded product, with high rigidity and excellent surface appearance, and having a complicated three-dimensional shape can be produced by a single process at high productivity. Even a molded product having a complicated three-dimensional shape can be obtained by integral molding in the present invention. Housing for electrical and electronic equipment can preferably be provided by the present invention. Brief Description of Drawings
[00014] Fig. 1 is a perspective view of a first embodiment of the present invention.
[00015] Fig. 2 is a perspective view of a second embodiment of the present invention.
[00016] Fig. 3 is a three-dimensional drawing (cross-sectional view) of the second embodiment of the present invention.
[00017] Fig. 4 is a junction of a horizontal part and a vertical part in the first embodiment of the present invention.
[00018] Fig. 5 is a cross-sectional photograph of a layer structure of the junction of a horizontal part and a vertical part in the first embodiment of the present invention. Mode for carrying out the invention
[00019] The present invention relates to a molded product consisting of a fiber reinforced composite material consisting of a thermoplastic resin and discontinuous reinforced fiber contained therein. Modalities of the molded product of the present invention are described below, but the invention is not limited to those modalities. Fiber reinforced
[00020] Fiber reinforced in fiber reinforced composite material constituting a molded product is not particularly limited. At least one selected from the group consisting of carbon fiber, an aramid fiber, a polyester fiber and glass fiber is preferably used. For uses that require strength and rigidity, carbon fiber, glass fiber and aramid fiber are preferably used and, preferably, carbon fiber. For uses that require conductivity, a carbon fiber is preferably used and, preferably, a carbon fiber coated with a metal such as nickel is used. For uses that require electromagnetic wave transmission, an aramid fiber and a polyester fiber are preferably used, and preferably an aramid fiber and glass fiber are used in terms of the balance between the electromagnetic wave transmission and force . For uses that require impact resistance, an aramid fiber and a polyester fiber are used. These fibers can be used in combination, types of reinforcement fibers can be selected depending on the part of the molded product and a molded product can be molded in a state where different reinforcement fibers are stacked. Thermoplastic resin
[00021] The amount of thermoplastic resin present in the fiber reinforced composite material constituting the molded product of the present invention is preferably from 50 to 1,000 parts by weight for 100 parts by weight of the reinforcement fibers. The amount of thermoplastic resin is more preferably from 55 to 500 parts by weight to 100 parts by weight of the reinforcement fibers and even more preferably, from 60 to 300 parts by weight to 100 parts by weight of the reinforcement fibers.
[00022] The thermoplastic resin constituting the molded product is not particularly limited. At least one selected from the group consisting of a vinyl chloride resin, a vinyl chloride resin, a vinyl acetate resin, a polyvinyl alcohol resin, a polystyrene resin, a styrene acrylonitrile resin (AS resin ), a styrene-butadiene-acrylonitrile resin (ABS resin), an acrylic resin, a methacrylic resin, a polyethylene resin, a polypropylene resin, a polyamide resin 6, a polyamide resin 11, a polyamide resin 12, a polyamide resin 46, a polyamide resin 66, a polyamide 610 resin a polyacetal resin, a polycarbon resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a polybutylene terephthalate resin, a polyarylate resin , a polyphenyl ether resin, a polyphenylene sulfide resin, a polysulfone resin, a polyether sulfone resin, a polyether ether ketone resin, a polylactic resin and a mixture (resin composition) d and two or more selected types of these resins are preferred. At least one selected from the group consisting of a composition of polycarbonate resin and a polyester resin, a composition of a polycarbonate and an ABS resin, a composition of a polyphenylene ether resin and a polyamide resin, a composition of a resin of polyamide and an ABS resin, and a composition of a polyester resin and a polyamide resin is most preferred as a resin composition.
[00023] Functional fillers and additives can be contained in the fiber-reinforced composite material in an amount that the object of the present invention is not impaired. Examples of the same include organic / inorganic fillers, a flame retardant, a UV resistant agent, a pigment, a mold release agent, a softener, a plasticizer and a surfactant, but not limiting. In particular, high flame retardancy is sometimes necessary in the use of electronic and electrical equipment and in the use of automobiles. Therefore, a flame retardant is preferably contained in a thermoplastic resin. Conventional flame retardants can be used as a flame retardant in the present invention, and the flame retardant used is not particularly limited, as long as it can transmit flame retardancy in the thermoplastic composition of the present invention. Specific examples of flame retardancy include a phosphorous flame retardant, a nitrogen flame retardant, a silicone compound, an organic alkali metal salt, an organic alkaline earth metal salt and a bromine flame retardant. These flame retardants can be used alone or in combination with two or more of these. The content of the flame retardant is preferable from 1 to 40 parts by weight, and more preferable, from 1 to 20 parts by weight, for 100 parts by weight of the resin in terms of balance of physical properties, malleability and flame retardancy. Reinforced fiber contained in the molded product
[00024] The reinforcement fibers contained in the molded product of the present invention are characterized in the ratio of the reinforced fiber bundles A consisting of the reinforcement fibers of the critical number of single fiber or more defined by formula (1): critical number of single fiber = 600 / D (1) where D is the average fiber diameter (μm) of a single reinforced fiber, for the total amount of reinforcement fibers in the molded product is 20% by volume or more and less than 90% by volume . In the molded product, single fibers or fiber bundles, each consisting of reinforcement fibers less than the critical single fiber number, are present as reinforcement fibers different from the fiber reinforced bundle A.
[00025] That is, the molded product of the present invention is characterized in that the amount of reinforced fiber bundles constituted by the reinforcing fibers of the single or more defined critical fiber number, depending on the average fiber diameter is 20% by volume or more, and less than 90% by volume, in other words, the bundle of reinforcement fibers consisting of a specific number or more of the unique reinforcement fibers obtained by controlling the degree of openness, and open reinforcement fibers different from the fiber bundles enhanced are contained in a specific reason.
[00026] Where the ratio of fiber-reinforced bundles A to the total amount of reinforcement fibers is less than 20% by volume there is an advantage that a molded product having excellent surface appearance is obtained, but a molded product having excellent mechanical properties is difficult to obtain. Where the ratio of fiber-reinforced bundles A is 90% by volume or more, a thickness of wrapped portions of the fibers is thick locally, and a thin-wall molded product cannot be obtained. The fiber-reinforced beam ratio is more preferably 30% by volume or more, and less than 80% by volume.
[00027] The molded product is further characterized in that the average number N of the reinforcement fibers in the bundles of reinforced fiber Each consisting of the reinforcement fibers of the critical number of single fiber or more satisfies the following formula (2): 0, 7x104 / D2 <N <1x105 / D2 (2) where D is an average fiber diameter (μm) of the reinforcement fibers.
[00028] Above all, the average number N of the reinforcement fibers in the bundles of reinforced fiber Each consisting of the reinforcement fibers of the critical number of single fiber or more is less than 6x104 / D2.
[00029] Specifically, if the reinforcement fibers in the molded product are carbon fibers and an average carbon fiber fiber diameter is 5 to 7 μm, the critical single fiber number is 86 to 120, and if the average fiber diameter of the carbon fibers is 5 μm, the average number of fibers in the fiber bundle is more than 280 and less than 4,000. Above all, the average number of fibers in the fiber bundle fibers is greater than 142 and is less than 2,040. Above all, the average number of fibers is preferably 300 to 1,500 and more preferably 300 to 800,
[00030] In case the average number N of fibers in the bundles of fiber reinforced A is less than 0.7x104 / D2, it becomes difficult to obtain a molded product having high fiber volume fraction (Vf). In case the average number N of the fibers in the reinforced fiber bundles A is 1x105 / D2 or more, thick portions can be formed locally in the molded product, which can cause voids. When it is desired to obtain a molded product with a final wall of 1 mm or less, the use of fibers simply separated results in a great inequality in the weight of the fiber area, failing to obtain good physical properties. Also, when all fibers are open, it can be easy to obtain a thinner product, but the wrapping of the fibers is increased and a product having a higher fraction of riba volume is not obtained. A molded final wall product having a high rate of physical property development can be obtained containing reinforced fiber bundles Each consisting of the reinforced fiber of the critical fiber number single or more defined by formula (1) and reinforcement fibers ( B) in a state of individual single fibers or made up of reinforcement fibers (B) in a state of individual single fibers or made up of reinforcement fibers less than the critical number of single fiber in the molded product. The molded product of the present invention can be of various thicknesses, and a thin-walled molded product having a thickness of about 0.2 to 1 mm can preferably be obtained.
[00031] The molded product can preferably be manufactured by compression molding, a random mat, consisting of reinforcing fibers, and a thermoplastic resin. The open state of the reinforcement fibers in the molded product substantially maintains the state in the random mat. The reinforcement fibers contained in the molded product can be properly adjusted by controlling the ratio of the reinforced fiber bundles A in the random mat and the average number N of the reinforcement fibers in the reinforced fiber bundles A in the random mat, so that the ratio of the bundles of reinforced fiber A in the molded product. A preferred method is described herein to control the ratio of reinforced fiber bundles A and the average number of reinforcement fibers therein, in the reinforcement fibers in the random mat.
[00032] The reinforcing fibers contained in the molded product of the present invention are staple fibers. The average fiber length of the fibers contained in the molded product is preferably 5 to 100 mm. A molded product consisting of a fiber reinforced composite material containing reinforcement fibers having a certain degree of fiber length can be provided by a preferred method for making the molded product of the present invention described herein. The molded product develops not only static strength and rigidity, but high physical properties for impact loading and fatigue loading over a long period of time. In addition, even in the case of molding a molded product having a complicated shape, it is difficult to interrupt the orientation of the reinforcement fibers, the reinforcement fibers orient two-dimensionally in one plane, and it is possible to maintain the isotropy. The average fiber length of the reinforcement fibers is preferably from 10 to 100 mm, more preferably from 15 to 100 mm, even more preferably from 15 to 80 mm and even more preferable from 20 to 60 mm.
[00033] The molded product of the present invention includes the wrapper where a part of the molded product is reinforced with a unidirectional or similar material. In the case of having a reinforced layer comprising a layer of unidirectional material in addition to the fiber reinforced composite material (larger part) consisting of a thermoplastic resin and staple reinforcement fibers contained therein, the above definition of the reinforcement fibers contained in the molded product is relates to the larger part, excluding the reinforced layer made of unidirectional and similar material. Molded product
[00034] The molded product preferably has a horizontal part and a vertical part that extends in a longitudinal direction to the horizontal direction. The vertical part may not be strictly a right angle as long as the vertical part extends in the longitudinal direction towards the horizontal part, and may have an angle to ensure an optional angle or an exit angle from a mold such that the intention of the present invention is not impaired. In this case, the annulus between the horizontal part and the vertical part is preferably 30 to 90 ° and more preferably 40 to 85 °. The optional chamfer and curvature can be added between the horizontal part and the vertical part in such a way that the intention of the present invention is not impaired. A chamfer size and curvature are not particularly limited. In the case of chamfering, C 0.2 to 10 mm is preferably used, and in the case of curvature, R 0.2 to 10 mm is preferably used.
[00035] In the case where the use of the molded product has the function of an external product plate, such as a housing or a panel-shaped member, a plurality of portions are preferably present on the same side of the surface of the horizontal part. Horizontal part
[00036] In the molded product of the present invention, the horizontal part means a part that substantially has a flat surface and forms a base for the vertical part, and an example of this includes a ceiling or base wall of a housing or a shaped member panel. It is not necessary for the horizontal part to have a completely flat surface and may partially have unevenness or granules. The height and width of the inequality and granules are not particularly limited. The height of 0.5 to 10 times the value of the thickness of the horizontal part that constitutes the base is desired. The horizontal part may have holes that go through for ventilation, screw tightening, connection and the like. In this case, the holes can be formed in a mold using a shearing machine or similar, simultaneously with the molding of the molded product, and can be formed by drilling, cutting or similar as a post-processing. The thickness of the horizontal part is not particularly limited. The thickness is preferably 0.2 to 5 mm and more preferably, 1 to 3 mm. It is not necessary for the thickness of the horizontal part to be uniform, and it can be partially increased or decreased. In this case, the thickness increase and decrease range is not particularly limited. The range is preferably from 30 to 300% and, more preferably, from 50 to 200%, with respect to the thickness of the horizontal part constituting the base. The thickness can be changed gradually and can be continuously changed with a cone or a curvature. The thickness is preferably changed continuously in order to avoid stress concentration. Vertical part
[00037] In the molded product of the present invention, the vertical part means a part extending in a longitudinal direction on the same side as the horizontal direction, and examples of this include a side wall, a rib, a protuberance, an assembly and an articulation of a housing or a molded panel member. The height of the vertical part is not particularly limited. The height is preferably 1 to 300 mm, and more preferably 5 to 100 mm. The height of the vertical part is not necessary to be uniform, and can be locally raised or reduced. The range of height increase and decrease of the vertical part is not particularly limited, and is preferably 10 to 90%, and more preferably 20 to 80%, with respect to the maximum height. The thickness of the vertical part is not particularly limited. The thickness can be the same or different from the horizontal part. Since the vertical part is required to be even more complicated in many cases as compared to the horizontal part, the thickness of the vertical part is preferably 0.2 to 100 mm, and more preferably 1 to 50 mm. The thickness of the vertical part is not required to be uniform, and can be locally raised or reduced. In this case, the thickness increase and reduction range is not particularly limited. The range is preferably 20 to 500%, and more preferably 50 to 200%, with respect to a standard thickness of the vertical part. The thickness can be changed in stages, and can be changed continuously with a cone or a curvature. The thickness is preferably changed continuously in order to avoid stress concentration. The vertical part preferably has an angle to hold an exit angle of a mold to such an extent that the intention of the present invention is not impaired. The exit angle of a mold is preferably 1 to 45 °, and more preferably 5 to 10 °. In the case that the vertical part is a protuberance or an assembly, a metallic part such as a helisert or a nutsert can be shaped by insertion into these. The vertical part may have partial and granular inequality. In this case, it should be noted that an exit angle from a mold can be safe. The vertical part can have a through hole for ventilation, screw fixation, wiring and the like, can form holes using a cutting machine, and can form holes by drilling, drilling, cutting or the like as post-processing. Formation of the molded product layer
[00038] It is preferred that the horizontal part and the vertical part have an X layer in which the reinforcement fibers are isotropic in a plane and are bidimensionally oriented, to obtain a molded product with a thin wall and light weight, having high rigidity and having excellent appearance, which is the aim of the present invention. The term "are isotropic in a plane and are two-dimensionally oriented" in the present invention means that the reinforcing fibers that make up the fiber-reinforced composite material have a primary orientation direction of a fiber axis on a tangential surface of the fiber composite material reinforced, and the ratio obtained by dividing the higher value by the lower value between the values of the stress module measured in two directions at right angles to each other in its plane does not exceed 2. The fact that the main orientation direction of the fiber axis is present on a tangential surface of the fiber reinforced composite material can be confirmed by the reinforcement fibers in the fiber reinforced composite material are arranged in a shape of the layer when observing the cross section of the fiber reinforced composite material.
[00039] It is further preferred that a junction between the horizontal part and the vertical part has at least two types selected from the group consisting of a layer X in which the reinforcement fibers are isotropic in a plane and are bidimensionally oriented, one layer Y in which the reinforcement fibers are continuously oriented horizontally and vertically, and a layer Z in which the reinforcement fibers are not bidimensionally oriented in a plane and are not continuously oriented horizontally and vertically. The ratio of the respective layers is not particularly limited. In the case of a thin-walled product having a simple shape, the X and Y ratios are high and the Z ratio is reduced. In the case of a thick product having a complicated shape, the X and Y ratios are reduced, and the Z ratio is high. In the case of the former, the ratios of X and Y in the thickness of the horizontal part are preferably 1 to 45%, respectively. In the case of the latter, the X and Y ratios in the thickness of the horizontal part are preferably 1 to 30%. This can guarantee the strength of the junction between the horizontal and vertical parts. In addition, light weight and high rigidity in the thin wall parts are obtained, and the flow of the fiber capable of forming a complicated three-dimensional shape is obtained while minimally guaranteeing the X layer that is isotropic in one plane and the reinforced fiber is three-dimensionally oriented, in the parts having great thickness. To obtain the X, Y and Z layer ratios within the molded product, it is important that the reinforcement fibers contained in the molded product include the bundle of reinforcement fibers A each consisting of the reinforced fiber of the critical single fiber number or more defined by the following formula (1), the ratio of this to the total amount of reinforcement fibers in the molded product is 20% by volume or more, and less than 90% by volume, and the average number N of the reinforcement fibers in the reinforcement fibers A meet the following formula (2). In addition, it is more preferred that the average fiber length is 5 to 100 mm to ensure a layer in which the reinforcing fibers are isotropic in one plane and are bidimensionally oriented even in a molded product having a complicated shape. Critical single fiber number = 600 / D (1) 0.7x104 / D2 <N <1x105 / D2 (2) where D is an average fiber diameter (μm) of the reinforcement fibers.
[00040] In the molded product in which a plurality of the upper parts are present on the same side of the plane to the horizontal parts as described above, it is preferred that the X layer in which the reinforcement fibers are isotropic in one plane and are bidimensionally oriented is continuously present in a plane of the horizontal part facing the upper parts. By this constitution, not only is a molded product being thin-walled and light-weight, and having high rigidity, but the appearance of the surface of a corresponding part on an external product plate can be improved. This layer constitution can still preferably be obtained by controlling the molding conditions in the compression molding described in this document.
[00041] To improve the appearance of the surface of a molded product, it is possible to adhere a decorative film on one side of the outer surface of the horizontal part and / or the upper parts. Examples of the decorative film include a transfer sheet having a desired decorative pattern as characters, graphic or pattern formed on it, a painted label and a painted film. A method of transferring a decorative pattern from the decorative film onto a surface of a molded product or adhering or fusing the decorative film itself is generally known. In this case, a layer to incorporate the unevenness of the surface of a molded product can be formed between the decorative film and the molded product. The decorative film can be adhered as a post-processing, and can be previously defined in a mold to press and integrally mold with a fiber reinforced composite material.
[00042] In the event that a large load acts on the molded product, it is possible to reinforce a part of the horizontal part and / or the vertical part with a unidirectional material. In this case, it is preferred that the unidirectional material is disposed on an external surface of the molded product, and it is still preferred from the perspective of masonry suppression during molding that the unidirectional materials are arranged both on the front and the horizontal surface of the molded product. to form a sandwich structure. The thickness of the unidirectional material is not particularly limited. The thickness is preferably 5 to 100%, and more preferably 10 to 50%, with respect to the thickness of the fiber reinforced composite material formed from a random mat. The limitations of the reinforced fiber bundle and the average fiber length of the reinforcement fibers contained in the molded product are limitations in the main parts of the molded product excluding parts such as the unidirectional material.
[00043] Unidirectional material means a material that continuous reinforcing fibers having a length of 100 mm or more are aligned in one direction on a thermoplastic resin. The type of the thermoplastic resin can be the same or different from the thermoplastic resin contained in the fiber reinforced composite material. The one-way material used in the present invention can be a material obtained by stacking a plurality of continuous reinforcing fibers, and can be a multi-axial wool fabric in which a material (material based on the multi-axial wool fabric) obtained forming a bundle of continuous reinforcing fibers in a blade shape and stacking the blades with the change of an angle is sewn with a sewing thread like a nylon thread, a polyester thread or a fiberglass thread passing the sewing thread through the body stacked in a direction of thickness and alternate between a front side and a rear side of the body stacked by the direction of the surface. In the unidirectional material, the amount of the thermoplastic resin is preferably 50 to 1,000 parts by weight per 100 parts by weight of the reinforcement fibers. The amount of the thermoplastic resin is more preferably 55 to 500 parts by weight, and even more preferably 60 to 300 parts by weight, per 100 parts by weight of the reinforcement fibers. Random blanket
[00044] A method for making a molded product of the present invention is not particularly limited. The molded product is preferably obtained by compression molding a random mat consisting of reinforcing fibers and a thermoplastic resin. The random blanket for obtaining the molded product consists of reinforcement fibers having a fiber length of 5 to 100 mm and a thermoplastic resin, and it is preferred that the fiber weight of the reinforcement fibers is 25 to 3,000 g / m2 , the bundle ratio of reinforcement fibers A consisting of single reinforcement fibers of the critical single fiber number or more defined by the following formula (1) to the total amount of reinforcement fibers in the blanket is 20% by volume or more, and less than 90% by volume, and an average number N of the reinforcement fibers in the reinforced fiber bundle A satisfies the following formula (2): critical single fiber number = 600 / D (1) 0.7x104 / D2 <N < 1x105 / D2 (2) where D is an average fiber diameter (μm) of the reinforcement fibers.
[00045] In a plane of the random blanket, the reinforcement fibers are not oriented in a specific direction, and are dispersed and arranged in random directions. The random blanket is a plane isotropic material. In the case that a molded product is obtained from the random mat, the isotropy of the reinforcement fibers in the random mat is also maintained even in the molded product. The isotropy of the random mat and the molded product obtained can be qualitatively evaluated by obtaining the molded product from the random mat and determining the stress modulus ratio in both directions at right angles to each other. For the values of stress modulus in both directions in the molded product obtained, when the ratio obtained by dividing the highest value by the lowest value does not exceed 2, it is evaluated as isotropic. When the ratio does not exceed 1.3, it is assessed as being excellent in isotropy.
[00046] The fiber beach weight of the reinforcement fibers in the random blanket is within a range of 25 to 3,000 g / m2. The random blanket is useful as a prepreg, and several sand weights of the fiber can be selected in accordance with the desired mold.
[00047] The reinforcement fibers in the random blanket are discontinuous, and the average fiber length thereof is preferably 5 to 100 mm. The molded product of the present invention is characterized in that the reinforcement fibers having great length in an extension are contained, and the reinforcement function can be developed. The fiber length is represented by an average fiber length determined by measuring the fiber length of the reinforcement fibers in the obtained random blanket. A method for measuring an average fiber length includes a method in which the fiber lengths of 100 arbitrarily extracted fibers are measured up to a 1 mm unit using lead cylinders, and their average is obtained.
[00048] The average fiber length of the reinforcement fibers in the random mat is preferably 10 to 100 mm, preferably 15 to 100 mm, more preferably 15 to 80 mm, and even more preferably 20 to 60 mm. In a preferable method for cutting the reinforcement fibers described in this document, in the case of producing a random blanket by cutting the reinforcement fibers at a fixed length, the average length of the fiber is approximately equal to the length of the fiber cut.
[00049] In the random blanket, it is preferred that the reinforcement fiber bundle A ratio consisting of the reinforcement fibers of the critical single fiber number or more represented by the formula (1): critical single fiber number = 600 / D (1 ) where D is an average fiber diameter (μm) of the reinforcement fibers, the total amount of reinforcement fibers in the random blanket is 20% by volume or more, and less than 90% by volume. In the random blanket, single fibers or fiber bundles consisting of the reinforced fiber less than the critical single fiber number are present as the reinforcement fibers other than the reinforcement fiber bundle A in the random blanket.
[00050] The random blanket preferably contains the fiber reinforced bundle in which the amount of the fiber reinforcement bundle consisting of single reinforced fiber of the critical or more defined single fiber number depending on the average fiber diameter is 20% by volume or more , and less than 90% by volume, that is, the degree of openness of the reinforcement fibers is controlled and the bundle consists of a specific number or more of the reinforcement fibers, and the open reinforcement fibers other than the bundle reinforced fiber, for a specific reason.
[00051] Where the ratio of the bundle of reinforcement fibers A to the total amount of reinforcement fibers is less than 20% by volume, there is an advantage that a composite material having excellent surface appearance is obtained by molding a random mat, but a fiber reinforced composite material having excellent mechanical properties is difficult to obtain. Where the bundle ratio of reinforcement fibers A is 90% by volume or more, the thickness of the sloping part of the reinforcement fibers is locally high, and a thin-walled product is not obtained. The reinforcement fiber bundle A ratio is more preferably 30% by volume or more and is less than 80% by volume. The amount of the fiber reinforced bundle of 20 to less than 90% by volume can be obtained, for example, by controlling a blown air pressure in an opening step. In addition, the ratio can be controlled by adjusting a size of a fiber bundle to be subject to a cutting step, for example, by adjusting a bundle width and the number of unique fibers per width. Specifically, a method in which a width of a fiber bundle is extended or similar and the fiber bundle is subject to a cutting step, and a method in which a separation step is provided before the cutting step, are exemplified. In addition, a method in which a bundle of fiber is cut using a so-called separating knife in which many short blades are arranged, and a method of separating simultaneously with cut, are exemplified. The preferred conditions are described in the item of an opening step.
[00052] The average number N of fibers in the bundle of reinforcement fibers A consisting of the reinforced fiber of the critical single fiber number or more preferably satisfies the following formula (2): 0.7x104 / D2 <N <1x105 / D2 (4 ) where D is an average fiber diameter (μm) of the reinforcement fibers.
[00053] To achieve this, the average number N of fibers in the bundle of reinforcement fibers A is within the above range, the average number N of fibers can be controlled by adjusting a size of a fiber bundle to be subject to a cutting step, for example, beam width and the number of single fibers per width, in the preferred production method described in this document. Specifically, a method in which a fiber bundle width is extended or similar and the bundle is subjected to a cutting step, and a method in which a separation step is provided before a cutting step, are exemplified . In addition, the fiber bundle can be separated simultaneously with cutting.
[00054] The degree of dispersion of the cut of the fiber bundle, for example, by a pressure of blown air in the opening step can be adjusted to control the average number N of the reinforced single fibers in the bundle of reinforcement fibers A. The conditions Preferred are described in the items of the fiber opening step and the cutting step.
[00055] Specifically, in the case that an average diameter of the carbon fiber fiber constituting the random blanket is 5 to 7 μm, the critical single fiber number is 86 to 120, and in the case that an average diameter of the fiber carbon fibers is 5 μm, the average number of fibers in the fiber bundle is within a range greater than 280 to less than 4,000. Above all, the average number of fibers is preferably 600 to 2,500, and more preferably 600 to 1,600. In the case that the average fiber diameter of the carbon fibers is 7 μm, the average number of fibers in the fiber bundle is within a range greater than 142 to less than 2,040. Above all, the average number of fibers is preferably 300 to 1,500, and more preferably 300 to 800.
[00056] In the case that the average number N of fibers in the bundle of reinforcement fibers A is 0.7x104 / D2 or less, there is a case to be difficult to obtain a composite material having a high fraction of the fiber volume (Vf). In addition, In the case that the average number N of fibers in the bundle of reinforcement fibers A is 1x105 / D2 or more, a part having great thickness can be locally formed, which is likely to cause voids. In the case where the thin-walled composite material having a thickness of 1 mm or less is directed to be obtained, the use of just simply separated fibers results in a great unevenness in the fiber's sand weight to fail to obtain good physical properties. In addition, in the case that all fibers are open, it may be easy to obtain a finer one, but the confusion of the fibers is high to fail to obtain one having a high fraction of the fiber volume. A thin random mat having high physical properties can be obtained by the random mat in which the bundle of reinforcement fibers A constituted by the single reinforced fiber of the critical single fiber number or is defined by formula (1) and the reinforcement fibers (B) in a state of individual single fibers or less than the critical single fiber number are simultaneously present. The random blanket of the present invention can be of various thicknesses. Using this as a preform, a thin-wall molded product having a thickness of approximately 0.2 to 1 mm can preferably be obtained.
[00057] The random blanket of the present invention contains a solid thermoplastic resin, and forms a preform to obtain a fiber reinforced composite material. It is preferred in the random blanket that the thermoplastic resin is present in a fiber form and / or a particulate form. The random blanket is characterized in that the reinforcement fibers and a thermoplastic resin in the form of fiber and / or particulate form are present in a mixed state, and as a result, it is not necessary to fluidize the reinforcement fibers and the resin in a mold, and the resin impregnation can be easily carried out in the molding. The thermoplastic resin is preferably constituted in a fiber form or in a particulate form. The type of thermoplastic resin can be two or more types, and a fiber-shaped thermoplastic resin and a particulate-shaped thermoplastic resin can be used in combination.
[00058] In the case of the fiber form, a fineness is preferably from 100 to 5,000 dtex, and more preferably from 1,000 to 2,000 dtex, and an average length thereof is preferably from 0.5 to 50 mm, and more preferably from 1 to 10 mm.
[00059] In the case of particulate form, there is preferably exemplified a spherical shape, a strip shape or a cylindrical shape such as a granule. In the case of the spherical shape, there is preferably a body of revolution of a perfect circle or an ellipse, or an egg-like shape. In the case of spherical shape, the average particle size is preferably from 0.01 to 1,000 μm, more preferably from 0.1 to 900 μm and even more preferably from 1 to 800 μm. Although no particular limitation on particle size distribution, sharp distribution is more preferred for the purpose of obtaining a finer molded product. However, the desired particle size distribution obtained by an operation such as classification can be used.
[00060] In the case of the strip shape, a columnar shape such as a granule, a prismatic shape or a scale shape is preferred. A strip shape obtained by cutting a film in a narrow form is also preferred. In this case, the strip may have a certain degree of aspect ratio, but the preferred length has the same degree as in the case of the fiber shape. Method to produce the random blanket
[00061] The random mat used in the present invention is preferably produced through the following steps 1 to 3: 1. A step of cutting the reinforcement fibers; 2. a step of introducing the reinforcement fibers cut into a tube and blowing air into the fibers to open a bundle of fiber; and 3. a step of dispersing the open reinforcement fibers, simultaneously sucking the fibers together as a form of fiber or particulate thermoplastic resin, applying the reinforcement fibers and the thermoplastic resin, and fixing the reinforcement fibers and thermoplastic resin.
[00062] Each step is described in detail below. Cutting step
[00063] The method of cutting the reinforcement fibers is specifically a cutting step to cut the reinforcement fibers using a knife. The knife is preferably a rotary cutter or the like.
[00064] To obtain a desired size of a fiber bundle, a bundle having a slightly narrow filament width is preferably used as a bundle of fiber to be cut. Alternatively, it is preferred that the reinforcement fibers are cut in a longitudinal direction to reduce the width of a filament. In this case, it is preferred that the fiber bundle is cut to a specific length of the fiber and simultaneously the fiber bundle is cut in a longitudinal direction, using a cutter having a blade perpendicular to one direction of the fiber and a blade parallel to one direction of the fiber.
[00065] The rotary cutter used is preferably a spiral knife or a fiber separating knife, having a specified angle. Fiber opening step
[00066] The fiber opening step is specifically a step for introducing the cut reinforcement fibers into a tube, blowing air into the fibers, and thus opening a fiber bundle. The degree of opening can be appropriately controlled by air pressure, and the like. It is preferred in the opening step that air is blown directly into the fiber bundle at a wind speed of 1 to 1,000 m / sec, and more preferably 5 to 500 m / sec from a hole that blows compressed air, and so reinforcement fibers can still be completely opened. Specifically, a plurality of holes having a diameter of approximately 1 mm is formed in a tube that passes like the reinforcement fibers, a pressure of approximately 0.2 to 0.8 MPa is applied from the outside, and the compressed air is directly blown into the fiber bundle, so that the fiber bundle can be easily opened. Application step
[00067] The application step is an application step to disperse the open reinforcement fibers, simultaneously sucking the fibers together with a particulate form of thermoplastic resin or fiber, and simultaneously spraying the reinforcement fibers and the thermoplastic resin. The open reinforcement fibers and fiber-shaped or particulate-shaped thermoplastic resin are preferably simultaneously applied to a blade, specifically a breathable blade provided at the bottom of a fiber opening apparatus.
[00068] In the application step, the amount of the thermoplastic resin supplied is preferably 50 to 1,000 parts by weight per 100 parts by weight of the reinforcement fibers.
[00069] The reinforcing fibers and the fiber form or thermoplastic resin in particulate form are preferably pulverized to be bidimensionally oriented. The application method and the following fixation method are important for applying the open fibers while allowing them to be bidimensionally oriented. The method of applying the reinforcement fibers preferably uses a tapered tube having a tapered or similar shape. In a conical tube, air is dispersed to slow the flow of the tube, and the rotational force is given as the reinforcing fibers. The reinforcement fibers opened in the conical tube can preferably be dispersed and sprayed using the Venturi effect.
[00070] Reinforcement fibers and thermoplastic resin are preferably sprayed on a breathable blade having a suction mechanism for the next fixation step.
[00071] The reinforcing fibers and the thermoplastic resin are preferably sprayed on the random blanket as well. Fixing step
[00072] The application and fixation steps can be carried out simultaneously. The fixation step is a step to reduce the reinforcement fibers and thermoplastic resin, which are applied. The fibers are preferably fixed by suction of air from a lower part of the breathable blade. The sprayed thermoplastic resin together with the reinforcement fibers is fixed by air suction when the thermoplastic resin is a fiber form, and fixed with the reinforcement fibers even in a particulate form.
[00073] A highly two-dimensionally oriented blanket can be obtained by conducting the suction of a lower part through the breathable blade. The particulate form or fiber-shaped thermoplastic resin can be easily mixed with the reinforcement fibers by suctioning the thermoplastic resin using the negative pressure generated and also by the diffusion flow generated in the tube. The obtained random mat can be impregnated with the thermoplastic resin in a relatively short period of time, since the movement distance of the thermoplastic resin is short in the impregnation step, due to the thermoplastic resin being present in the vicinity of the reinforcement fibers. A breathable non-woven fabric having the same material as the matrix resin used is previously defined on a fixation part, and the reinforcement fibers and particles can be sprayed onto the non-woven fabric.
[00074] The application and fixation step is carried out simultaneously, that is, the fixation can be carried out during application.
[00075] The preferred method for producing a random mat as described above can provide a random mat having two-dimensional orientation, in which the ratio of fibers having a long three-dimensionally oriented axis is small. Compression molding
[00076] The method for molding a molded product of the present invention is not particularly limited. The method preferably includes arranging a random mat or a prepreg formed by the plate obtained by pressing a random mat, as a base material in a mold and compression molding of the base material.
[00077] Above all, the base material is arranged so that a charge rate of the following formula (5) is 25 to 100%, and is pre-molded. Load rate = 100x area of the base material (mm2) / projected area of the mold cavity (mm2) (5) where the projected area of the mold cavity means a projected area in a plotted direction.
[00078] In the event that high physical properties and appearance of the surface are required in the horizontal part of the molded product, the loading rate is preferably 80 to 100%. Where the load rate is less than 80%, the region where the X layer in which the reinforcement fibers are isotropic in a plane and are two-dimensionally oriented cannot be safe is high in the horizontal, and the rate of development of the properties physical and surface appearance tend to be reduced. Where the charge rate exceeds 100%, burr is generated at the edge of the molded product, and equalizer by machine processing or the like is required in post-processing. Thus, not only is a process complicated, but the loss is generated. When the loading rate is 80 to 100%, a lightweight molded product can be manufactured at high productivity while guaranteeing the X layer in which the reinforcement fibers are isotropic in a plane and are bidimensionally oriented, horizontally no loss of material and problematic equalizer.
[00079] Specifically, the molded product can be manufactured by going through the following step 1), and then the following step 2) or 2 '): 1) a thermoplastic resin in a random mat is melted under pressure, the thermoplastic resin is impregnated in a bundle of reinforced fiber and spaces between the single fibers of the reinforcement fibers, followed by cooling, and a prepreg formed by the plate is obtained; 2) the prepreg formed by the plate is heated at a melting point or higher or a transition point of glass or higher of the thermoplastic resin, a shape of the prepreg corresponds to that of a molded product to be obtained, and a single prepreg or layer prepreg is introduced into a mold kept lower than a melting point or lower than a glass transition point of the thermoplastic resin, followed by pressure and then cooling, which it is called cold pressure; and 2 ') the prepreg formed by the plate is introduced into a mold, compression molding is conducted while raising a temperature at a melting point or higher or a glass transition point or higher of the thermoplastic resin, and the mold is cooled less than a melting point or less than a glass transition point of the thermoplastic resin, which is called heat pressure.
[00080] In step 1), a plurality of random blankets can be superimposed to obtain a desired thickness and sand weight of the fiber, and the superimposed body can be pressed. Example
[00081] The present invention is described specifically by examples, but the invention is not limited by them. 1) Fiber bundle analysis reinforced in random blanket
[00082] The ratio of reinforcement bundles A to the total amount of reinforcement fibers in a blanket is obtained as follows.
[00083] A random blanket is cut to a size of 100 mm x 100 mm, and a thickness (Ta) and weight (Wa) are measured.
[00084] The fiber bundles are all extracted by forceps from the blanket cut, and classified in each diameter. In this example, the fiber bundles have been classified with a unit with a diameter of approximately 0.2 mm.
[00085] Length (Li), weight (Wi) and the number of fiber bundles (I) are measured at each classification, and recorded. For fiber bundles that are small to a certain extent that the bundles cannot be extracted by tweezers, it is the weight (Wk) of the bundle that is finally measured as a whole. In this case, a balance that can be measured up to 1 / 1,000 g is used. Particularly, in the case that the reinforcement fibers are carbon fibers and in the case that the fiber length is short, a weight of a fiber bundle is small, and the measurement becomes difficult. In this case, a plurality of classified fiber bundles are obtained, and the weight thereof is measured.
[00086] After the measurement, the following calculation is conducted. The number (Ni) of fibers in the individual fiber bundle was obtained from a fineness (F) of reinforcement fibers used by the following formula. Ni = Wi / (LixF)
[00087] The average number N of fibers in the bundle of reinforcement fibers A is determined by the following formula. N = ∑Ni / I
[00088] The volume (Vi) of the individual reinforcement fiber bundle and the ratio (VR) of the reinforced fiber bundle A in all reinforcement fibers were obtained by the following formulas using a fiber density (p) of the reinforcement fibers used. Vi = Wi / p VR = ∑Vi / Vax100 where Va is a volume of a blanket cut, and Va = 100x100xTa. 2) Analysis of the fiber bundle reinforced in the molded product
[00089] A molded product was heated in an oven at 500 ° C for approximately 1 hour to remove a resin, and was subjected to the same measurement as the method described in the random blanket above. 3) Analysis of fiber orientation in the molded product
[00090] After molding a composite material, fiber isotropy was confirmed by conducting a stress test based on an arbitrary direction of a molded plate and a direction perpendicular in the direction to measure the stress modulus, and the ratio (Eδ) is obtained by dividing the highest value in the measured values of the voltage module by the lowest value in it. A material has excellent isotropy as the reason for the elasticity 1 approaches. 4) Average length analysis of the fiber reinforcement fibers contained in the molded product
[00091] An average fiber length of the reinforcement fibers contained in the molded product obtained was obtained as follows. The molded product was heated in an oven at 500 ° C for approximately 1 hour to remove a resin. Lengths of 100 reinforcement fibers arbitrarily extracted were measured with a magnifying glass up to a 1 mm unit, and recorded. The average fiber length (La) was obtained from lengths (Li) of all reinforcement fibers measured by the following formula. La = ∑Li / 100 Reference Example 1
[00092] Carbon fibers (TENAX carbon fiber (trademark) STS40-24KS (fiber diameter: 7 μm, tensile strength: 4,000 MPa), manufactured by Toho Tenax Co., Ltd.) have been cut to length 20 mm at the opening, and were introduced into a taper tube at a feed rate of 300 g / min. Air was blown into the carbon fibers in the tapered tube to partially open the fiber bundle, and the carbon fibers were sprayed onto a table provided at the bottom of a tapered tube outlet. The PA66 fibers (T5 Nylon, 1400 dtex, manufactured by Asahi Kasei Fibras Corporation) dry cut to 2 mm were supplied as a matrix resin to the conical tube at a rate of 500 g / min, and sprayed simultaneously with the carbon fibers. Thus, a random blanket having a thickness of approximately 4 mm in which the carbon fibers having an average fiber length of 20 mm and PA66 were mixed. The shape of the reinforcement fibers in the random blanket was observed. As a result, a fiber axis of the reinforcement fibers is almost parallel to a plane, and the reinforcement fibers were randomly dispersed in a plane. The average fiber length (La), the reinforcement fiber bundle ratio A and the average number N of the random blanket fibers obtained were evaluated. As a result, the average fiber length (La) was 20 mm, the critical single fiber number defined by formula (1) was 86, the ratio of the reinforcement fibers bundle A to the total amount of fibers in the blanket was 35 %, and the average number N of the reinforcement fibers in the reinforcement fiber bundle A was 240,
[00093] The random blanket was heated to 2.0 MPa for 5 minutes by a pressure machine heated to 280 ° C to obtain a molded plate having a thickness of 0.8 mm.
[00094] The fraction of the volume of the molded plate fiber obtained was approximately 30% by volume. Reference Example 2
[00095] Carbon fibers (TENAX carbon fiber (trademark) IMS60-12K (average fiber diameter: 5 μm, fiber width: 6 mm), manufactured by Toho Tenax Co., Ltd.) have been cut to length 30 mm, and were introduced into a conical tube at a feed rate of 1,000 g / min. Air was blown into the carbon fibers in the tapered tube to partially open the fiber bundle, and the carbon fibers were sprayed onto a table provided at the bottom of a tapered tube outlet. PC resin (PANLI-TE (trademark) L-1225L, manufactured by Teijin Chemicals Ltd.) sprayed by freezing over an average particle diameter of approximately 1 mm was supplied as a matrix resin to the conical tube at a rate of 3,000 g / min, and sprayed simultaneously with the carbon fibers. Thus, a random blanket having a thickness of approximately 10 mm in which the carbon fibers having an average fiber length of 30 mm and PC were mixed. The shape of the reinforcement fibers in the random blanket was observed. As a result, a fiber axis of the reinforcement fibers is almost parallel to a plane, and the reinforcement fibers were randomly dispersed in a plane. The average length of the fiber (La), the ratio of the bundle of reinforcement fibers A and the average number N of fibers, of the random blanket obtained were evaluated. As a result, the average fiber length (La) was 30 mm, the critical single fiber number defined by formula (1) was 120, the ratio of the reinforced fiber bundle A to the total amount of fibers in the blanket was 80% , and the average number N of fibers in the bundle of reinforcement fibers A was 1,000. The random blanket was heated to 2.0 MPa for 5 minutes by a pressure machine heated to 300 ° C to obtain a molded plate having a thickness of 3 mm.
[00096] The volume fraction of the molded plate fiber obtained was approximately 20% by volume. Reference Example 3
[00097] Glass fibers (EX-2500 (average fiber diameter: 15 μm, fiber width: 9 mm), manufactured by Asahi Glass Co., Ltd.) were cut to a length of 50 mm, and were introduced into a conical tube at a feed rate of 1,200 g / min. Air was blown into the carbon fibers in the tapered tube to partially open the fiber bundle, and the carbon fibers were sprayed onto a table provided at the bottom of a tapered tube outlet. The PA66 fibers (T5 Nylon, 1400 dtex, manufactured by Asahi Kasei Fibras Corporation) with a 2 mm dry cut were supplied as a matrix resin to the conical tube at a rate of 1,300 g / min, and sprayed simultaneously with the carbon fibers. Thus, a random blanket having a thickness of approximately 6 mm in which the carbon fibers having an average fiber length of 50 mm and PA66 were mixed. The shape of the reinforcement fibers in the random blanket was observed. As a result, a fiber axis of the reinforcement fibers is almost parallel to a plane, and the reinforcement fibers were randomly sprayed in a plane. The average length of the fiber (La), the ratio of the bundle of reinforcement fibers A and the average number N of fibers, of the random blanket obtained were evaluated. As a result, the average fiber length (La) was 50 mm, the critical single fiber number defined by formula (1) was 40, the ratio of the reinforced fiber bundle A to the total amount of fibers in the blanket was 60%, and the average number N of fibers in the reinforced fiber bundle A was 60. The random mat was heated to 2.0 MPa for 5 minutes by a pressure machine heated to 280 ° C to obtain a molded plate having a thickness of 1, 6 mm.
[00098] The volume fraction of the molded plate fiber obtained was approximately 30% by volume. Reference Example 4
[00099] Carbon fibers (TENAX carbon fiber (trademark) STS40-24KS (fiber diameter: 7 μm, tensile strength: 4,000 MPa), manufactured by Toho Tenax Co., Ltd.) have been cut to length 20 mm while open, and were introduced into a conical tube at a feed rate of 300 g / min. Without blowing air into the carbon fibers in the tapered tube, the carbon fibers were sprayed onto a table provided at the bottom of a tapered tube outlet. The PA66 fibers (T5 Nylon, 1400 dtex, manufactured by Asahi Kasei Fibras Corporation) 2 mm dry cut were supplied as a matrix resin to the conical tube at a rate of 500 g / min, and sprayed simultaneously with the carbon fibers. Thus, a random blanket having a thickness of approximately 1 mm in which the carbon fibers having an average fiber length of 20 mm and PA66 were mixed. The average fiber length (La) and the reinforcement fiber bundle ratio A and the average number N of fibers, of the obtained random blanket were evaluated. As a result, the average fiber length (La) was 20 mm, the critical single fiber number defined by formula (1) was 86, the ratio of reinforcement fibers bundle A to the total amount of fibers in the blanket was 100 %, and the average number N of fibers in the fiber reinforced bundle A was 24,000,
[000100] The random blanket was heated to 2.0 MPa for 5 minutes by a pressure machine heated to 280 ° C to obtain a molded plate having a thickness of 0.8 mm.
[000101] The fraction of the volume of the molded plate fiber obtained was approximately 30% by volume. Example 1
[000102] Seven plates formed in Reference Example 1, heated to 280 ° C in an IR oven were superimposed, and the resulting superimposed body was arranged in a horizontal part of a mold having a shape shown in Fig. 1 and defined at 120 ° C so that the loading rate is 90%, and the compression molding was carried out under a pressure of 15 MPa. It could be confirmed by cross-sectional observation (10 times the zoom) that the molded product obtained was a molded product in which the resin and fibers were filled up to the end of the vertical part. The tension modulus of the horizontal and vertical parts of the molded product was measured. As a result, the ratio (Eδ) obtained by dividing the highest value of voltage modulus values measured in the two directions perpendicular to each other by the lowest value was 1.05, and it could be confirmed that the isotropy was maintained. In addition, a cross-sectional observation (10 times the zoom) was conducted to a root of the vertical part. As a result, as shown in Fig. 5, it could be confirmed that the X layer in which the reinforcement fibers are isotropic in a plane and are two-dimensionally oriented, the Y layer in which the reinforcement fibers are continuously oriented horizontally and in the vertical part, and the Z layer in which the reinforcement fibers are not bidimensionally oriented in a plane and are not continuously oriented horizontally and vertically, were present. The average fiber length (La), the bundle ratio of reinforcement fibers A and the average number N of fibers, of the horizontal part of the molded product obtained were evaluated. As a result, the average fiber length (La) was 20 mm, the critical single fiber number defined by formula (1) was 86, the ratio of the reinforcement fiber bundle A to the total amount of fibers in the molded product was 35%, and the average number N of fibers in the reinforced fiber bundle A was 240. Similarly, the average fiber length (La), the ratio of reinforcement fibers A bundle and the average number N of fibers, of the vertical part were evaluated. As a result, the critical single fiber number defined by formula (1) was 86, the average fiber length (La) was 19 mm, the ratio of reinforcement fibers A bundle to the total amount of fibers in the molded product was 40%, and the average number N of fibers in the bundle of reinforcement fibers A was 230, Example 2
[000103] Two plates formed prepared in Reference Example 2, heated to 300 ° C in an IR oven were superimposed, and the resulting superimposed body was arranged in a horizontal part of a mold having a shape shown in Fig. 1 and defined at 150 ° C so that the loading rate is 85%, and the compression molding was conducted under a pressure of 15 MPa. It could be confirmed by transversal observation (10 times the zoom) that the molded product obtained was a molded product in which the resin and fibers were filled up to the end of the vertical part. The tension module of the horizontal part and the vertical part of the molded product were measured. As a result, the ratio (Eδ) obtained by dividing a higher value of voltage modulus values measured in two directions perpendicular to each other by a lower value of the same was 1.07, and it could be confirmed that the isotropy was maintained. In addition, a cross-sectional observation (10 times the zoom) was conducted on a root of the vertical part. As a result, similar to Example 1, it could be confirmed that the layer X in which the reinforcement fibers are isotropic in a plane and are two-dimensionally oriented, the layer Y in which the reinforcement fibers are continuously oriented in the horizontal part and in the vertical, and in layer Z in which the reinforcement fibers are not bidimensionally oriented in a plane and are not continuously oriented horizontally and vertically, were present. The average fiber length (La), the bundle ratio of reinforcement fibers A and the average number N of fibers, of the horizontal part of the molded product obtained were evaluated. As a result, the average fiber length (La) was 29 mm, the critical single fiber number defined by formula (1) was 120, the ratio of the reinforcement fibers A bundle to the total amount of fibers in the molded product was 80%, and the average number N of fibers in the bundle of reinforcement fibers A was 1,000. Similarly, the average length of the fiber (La), the bundle ratio of reinforcement fibers A and the average number N of fibers in the vertical part were evaluated. As a result, the critical single fiber number defined by formula (1) was 86, the average fiber length (La) was 28 mm, the ratio of the reinforcement fiber bundle A to the total amount of fibers in the molded product was 80%, and the average number N of fibers in the bundle of reinforcement fibers A was 950, Example 3
[000104] The molded plate prepared in Reference Example 3, heated to 280 ° C in an IR oven was arranged in a horizontal part of a mold having a shape shown in Fig. 2 and set at 120 ° C so that the rate load is 99%, and compression molding was conducted under a pressure of 15 MPa. It could be confirmed by transversal observation (10 times the zoom) that the molded product obtained was a molded product in which the resin and fibers were filled at the end of a protuberance, a rib, a part of the frame and the like. The tension module of the horizontal part of the molded product was measured. As a result, the ratio obtained by dividing the highest value of voltage modulus values measured in two directions perpendicular to each other by the lowest value of the same was 1.05, and it could be confirmed that the isotropy was maintained. The tension modulus of the frame part of the molded product was measured. As a result, the ratio (Eδ) obtained by dividing the highest value of voltage modulus values measured in the two directions perpendicular to each other by the lowest value of the same was 1.07, and it could be confirmed that the isotope was maintained. In addition, a cross-sectional observation (10 times the zoom) was conducted on the vertical part of the frame part. As a result, similar to Example 1, it could be confirmed that the layer X in which the reinforcement fibers are isotropic in a plane and are two-dimensionally oriented, the layer Y in which the reinforcement fibers are continuously oriented in the horizontal part and in the vertical, and the Z layer in which the reinforcement fibers are not bidimensionally oriented in a plane, and are not continuously oriented horizontally and vertically, were present. The average fiber length (La), the bundle ratio of reinforcement fibers A and the average number N of fibers, of the horizontal part of the molded product obtained were evaluated. As a result, the average fiber length (La) was 50 mm, the critical single fiber number defined by formula (1) was 40, the ratio of the reinforcement fiber bundle A to the total amount of fibers in the molded product was 60%, and the average number N of fibers in the bundle of reinforcement fibers A was 60. Similarly, the average fiber length (La) the ratio of the reinforced fiber bundle A and the average number N of fibers, of the frame part have been examined. As a result, the critical single fiber number defined by formula (1) was 40, the average fiber length (La) was 48 mm, the ratio of the reinforcement fibers bundle A to the total amount of fibers in the molded product was 58%, and the average number N of fibers in the bundle of reinforcement fibers A was 60. Comparative example 1
[000105] The molding was carried out in the same way as in Example 1, except to use the molded plate prepared in Reference Example 4. The molded product obtained was a molded product in which the fluidization of the fiber could be visually confirmed in the vertical part, and the tension module of the vertical part was measured. As a result, the ratio (Eδ) obtained by dividing the highest value of the values of the voltage module measured in two directions perpendicular to each other by a lower value of the same was 2.1, and it can be confirmed that the isotropy was impaired. In addition, the cross-sectional observation (10 times the zoom) was carried out on a vertical root. As a result, layer X in which the reinforcement fibers are isotropic in one plane and are two-dimensionally oriented, and layer Z in which the reinforcement fibers are not two-dimensionally oriented in one plane and are not continuously oriented horizontally. and in the vertical part, they were not present, and only the Y layer in which the reinforcement fibers are continuously oriented in the horizontal part and in the vertical part was present. The average fiber length (La), the fiber reinforced bundle ratio A and the average number N of fibers, of the horizontal part of the molded product obtained were examined. As a result, the average fiber length (La) was 20 mm, the critical single fiber number defined by formula (1) was 86, the ratio of reinforcement fibers bundle A to the total amount of fibers in the molded product was 100%, and the average number N of fibers in the bundle of reinforcement fibers A was 24,000. Similarly, the average fiber length (La), the bundle ratio of reinforcement fibers A and the average number N of fibers, of the horizontal part were examined. As a result, the critical single fiber number defined by formula (1) was 86, the average fiber length (La) was 20 mm, the ratio of the reinforcement fibers A bundle to the total amount of fibers in the molded product was 100%, and the average number N of fibers in the bundle of reinforcement fibers A was 24,000, Industrial applicability
[000106] The molded product of the present invention can be used in the wide range as housings for electrical and electronic equipment, parts for automotive parts, parts for medical equipment, parts for aircraft, building materials and parts for industries in general, and is particularly preferred to use in housings for electrical and electronic equipment. Description of reference numerals and signs 1 Horizontal part 1A Horizontal part (partial inequality, present granules) 1B Horizontal part (through hole) 1C Horizontal part (change in plate thickness is present) 2 Vertical part 2A Vertical part (side wall ) 2B Vertical part (rib) 2C Vertical part (protuberance) 2D Vertical part (assembly) 2E Vertical part (joint) 3 Junction 4 Layer X in which the reinforcement fibers are isotropic in a plane and are bidimensionally oriented 5 Layer Y in which the reinforcement fibers are continuously oriented horizontally and vertically 6 Z layer in which the reinforcement fibers are not bidimensionally oriented in a plane, and are not continuously oriented horizontally and vertically

权利要求:
Claims (11)
[0001]
1. Molded product characterized by the fact that it comprises a reinforced composite material including staple reinforcement fibers contained in a thermoplastic resin, in which the reinforcement fibers contained in the molded product have an average fiber length of 5 to 100 mm and include (i ) a fiber reinforced bundle (A) comprising the reinforcement fibers of a critical single fiber number defined by formula (1) or more, a ratio of the fiber reinforced bundle (A) to a total amount of the reinforcement fibers in the product is 20% by volume or more, and less than 90% by volume, and an average number (N) of the reinforcement fibers in the reinforced fiber bundle (A) satisfies the following formula (2), and (ii) the reinforcement fibers (B), which is a bundle consisting of reinforcement fibers lower than the critical number of single fibers: critical single fiber number = 600 / D (1) 0.7xW4 / D2 <N <1xW5 / D2 (2) where D is an average fiber diameter (μm) of the reinforcement fibers; the molded product comprising: a horizontal part; and a vertical part extending in a longitudinal direction to the horizontal part; wherein the horizontal part and the vertical part have a layer (X) in which the reinforcement fibers are isotropic in a plane and are bidimensionally oriented.
[0002]
2. Molded product according to claim 1, characterized by the fact that the horizontal part is a ceiling or bottom wall of a housing or a molded panel member.
[0003]
3. Molded product according to claim 1, characterized by the fact that the vertical part is at least one member selected from the group consisting of a side wall, a rib, a protuberance, an assembly and a joint of a housing or a molded panel member.
[0004]
4. Molded product according to claim 1, characterized by the fact that a junction between the horizontal part and the vertical part has at least two types selected from the group consisting of a layer (X) in which the reinforcement fibers are isotropic in a plane and are bidimensionally oriented, a layer (Y) in which the reinforcement fibers are continuously oriented horizontally and vertically, and a layer (Z) in which the reinforcement fibers are not bidimensionally oriented in a plane and are not continuously oriented horizontally and vertically.
[0005]
5. Molded product, according to claim 1, characterized by the fact that a plurality of the upper parts is present on the same side of the plane in the horizontal part.
[0006]
6. Molded product according to claim 5, characterized by the fact that the layer (X) in which the reinforcement fibers are isotropic in one plane and are bidimensionally oriented is continuously present in a plane facing the upper parts in the horizontal .
[0007]
7. Molded product according to claim 1, characterized by the fact that it still comprises a layer including a unidirectional material in which the continuous fibers are arranged along a direction in the thermoplastic resin, in the horizontal and / or in the vertical part.
[0008]
8. Molded product according to claim 1, characterized by the fact that the reinforced fiber is at least one selected from the group consisting of a carbon fiber, an aramid fiber, a polyester fiber and a glass fiber.
[0009]
9. Use of the molded product, as defined in claim 1, characterized by the fact that it is like housings for an electrical and electronic equipment.
[0010]
10. Method for manufacturing the molded product, as defined in claim 1, characterized in that it comprises the step of obtaining the molded product by compression molding a random mat, wherein the random mat comprises reinforcing fibers having a fiber length from 5 to 100 mm and a thermoplastic resin, a fiber weight of the reinforcement fibers are 25 to 3,000 g / m2, and a reinforced fiber bundle ratio (A) comprising the reinforcement fibers of a single fiber number critical value defined by the following formula (1) or more in a total amount of reinforcement fibers in the blanket is 20% by volume or more, and less than 90% by volume, and an average number (N) of the reinforcement fibers in the bundle fiber reinforced (A) meets the following formula (2): critical single fiber number = 600 / D (1) 0.7x104 / D2 <N <1x105 / D2 (2) where D is an average fiber diameter ( μm) of the reinforcement fibers.
[0011]
11. Method for manufacturing the molded product, according to claim 10, characterized by the fact that it still comprises: arranging the heated random blanket in a mold so that a loading rate represented by formula (3) is 25 to 100% ; and compression molding of the random mat: load rate = 100x area of the base material (mm2) / projected area of the mold cavity (mm2) (3) in which the projected area of the mold cavity means an area projected in a drawn direction.

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-01-14| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-07-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/08/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2011-041684|2011-02-28|

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JP2011041684|2011-02-28|

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PCT/JP2011/070313|WO2012117593A1|2011-02-28|2011-08-31|Molded body comprising fiber-reinforcing composite material|

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