巴西专利BR112013019395B1 RANDOMIC MAT, METHOD TO PRODUCE RANDOMIC MAT AND COMPOSITE MATERIAL REINFORCED WITH CARBON FIBER

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专利摘要:
RANDOMIC TRACK AND REINFORCED FIBER COMPOSITE MATERIAL. The purpose of the present invention is to provide a random mat used as a preform for a shaped product of fiber reinforced composite material. The random mat of the present invention including: reinforcement fibers having an average fiber length of 5 to 100 mm; and a thermoplastic resin, where a density of reinforcement fibers is 25 to 3000 g / m2, for a bundle of reinforcement fibers (A) including reinforcement fibers equivalent to, or more than, a critical number of single fibers defined by formula (1), a ratio of the bundle of reinforcement fibers (A) to a total amount of reinforcement fibers on the mat is 30% by volume to less than 90% by volume, and an average number (N) of the fibers by reinforcement in the bundle of reinforcement fibers (A) meets formula (2): critical number of single fibers = 600 / D (1) 0.7x104 / D2 1x105 / D2 (2) where D is an average fiber diameter (pm) reinforcement fibers.
公开号:BR112013019395B1
申请号:R112013019395-6
申请日:2011-08-31
公开日:2021-04-06
发明作者:Yuhei Konagai；Katsuyuki Hagihara；Naoaki Sonoda；Noboru Okimoto
申请人:Teijin Limited；
IPC主号:

专利说明:

[0001] [001] The present invention relates to a random mat usable as a preform of a shaped product made of fiber reinforced composite material, and a fiber reinforced composite material obtained therefrom. Background of the Technique
[0002] [002] Fiber reinforced composite materials where carbon fibers, aramid fibers, glass fibers or the like are used as reinforcement fibers have been widely used for structural materials, such as aircraft and automobiles, and industry in general or use in sports, such as tennis rackets, golf club rods and fishing rods, using its high specific strength and specific modulus of elasticity. As forms of reinforcing fibers, there are fabrics produced using continuous fibers, UD sheets with unidirectionally aligned fibers, random sheets produced using cut fibers, non-woven fabrics and the like.
[0003] [003] Generally, in the case of fabrics made of continuous fibers, UD sheets and the like, complicated lamination stratification steps such as stratification at various angles, for example, at 0 / + 45 / -45 / 90, due to the anisotropy of fibers, as well as flat - symmetrical lamination to prevent warping of shaped products, have become one of the factors that increase the cost of fiber reinforced composite materials.
[0004] [004] In the same way, a relatively inexpensive fiber-reinforced composite material can be obtained using a previously isotropic random mat. This random mat can be obtained through a "spray-up" system (dry production method) in which spreading cut reinforcement fibers alone or spreading cut reinforcement fibers together with a thermosetting resin are carried out at the same time in a mold. molding, or a papermaking (wet method) of adding reinforcement fibers previously cut to an aqueous paste containing a binder, and followed by a papermaking process. Use of the dry production process can provide the random conveyor more cheaply, because a rig is relatively small in size.
[0005] [005] As the dry production process, a continuous fiber cutting technique is commonly used and concurrently spreading the cut fibers, and a rotary cutter is used in many cases. However, when the distance between the cutter blades is increased in order to increase the length of the fiber, the cutting frequency decreases, and therefore resulting in discontinuous discharge of the fibers from the cutter. For this reason, the uneven fiber beach weight of the belt fibers occurs locally. In particular, when the mat having a low fiber fiber sand weight is prepared, the unevenness in thickness becomes significant, which causes a problem of deteriorated surface appearance.
[0006] [006] On the other hand, another factor that increases the cost of fiber-reinforced composite materials is that the molding time is long. Usually, the fiber-reinforced composite material is obtained by heating and pressurizing a material called prepreg where a reinforcement fiber-based material is previously impregnated with a thermosetting resin, using an autoclave for 2 hours or more. In recent years, an RTM molding process has been proposed in which a reinforcement fiber-based material not impregnated with a resin is placed in a mold, and then a thermosetting resin is poured into it, and the molding time has been substantially reduced. reduced. However, even when the RTM molding process is adopted, it takes 10 minutes or more before a part is molded.
[0007] [007] For this reason, a composite material using a thermoplastic resin as a matrix, instead of conventional thermosetting resin, is attracting attention. However, the thermoplastic resin generally has a high viscosity compared to the thermosetting resin, so that the time to impregnate the molten resin in the fiber-based material becomes long. As a result, there has been an issue where the takt time to mold increases.
[0008] [008] As a technique for solving these problems, a technique called thermoplastic stamping molding (TP-SMC) is proposed. This is a molding process in which cut fibers previously impregnated with a thermoplastic resin are heated to a melting point or more or a flowable temperature or more of the resin and placed in a part of a mold, immediately after the mold is closed, and the fibers and resin are allowed to flow into the mold, whereby obtaining a product form, followed by cooling to form a form product. According to this technique, molding is possible for a short period of time such as about 1 minute using fibers previously impregnated with the resin. There are Patent Documents 1 and 2 regarding processes for producing bundles of cut fibers and molding materials. However, these are methods using molding materials known as SMC or stamping sheets. In such a thermoplastic stamping molding, the fibers and resin are allowed to flow into the mold, so that there may be failure problems for producing a thin-walled one and the fiber orientation is disturbed as the orientation becomes out of shape. control.
[0009] [009] As a means for the production of a thin-walled one without allowing fiber flow, a technique for preparing a thin sheet of reinforcement fibers through a papermaking process is proposed, followed by sheet impregnation. with a resin to prepare a prepreg (Patent Document 3). In the papermaking process, the reinforcement fibers are allowed to be homogeneously dispersed in an aqueous dispersion, so that the reinforcement fibers are in a single fiber form. (Patent Document 1) JP-A-2009-114611 (Patent Document 2) JP-A-2009-114612 (Patent Document 3) JP-A-2010-235779 Exhibition of the Invention Problems the Invention Solves
[0010] [010] Problems for the invention to solve refer to a random mat used as a preform of a fiber-reinforced composite product and a fiber-reinforced composite material obtained therefrom. The random mat of the invention is characterized in that a thermoplastic matrix resin can be easily impregnated in bundles of reinforcement fibers and between single fibers of the reinforcement fibers in the random mat, and therefore being able to provide a fiber reinforced composite material that it is thin in thickness and excellent in physical mechanical properties. Troubleshooting Means
[0011] [011] In the invention, it was found that a thermoplastic matrix resin can be easily impregnated through the formation of a random mat including a thermoplastic resin and reinforcement fibers satisfying specific conditions of beam formation or opening, which makes it possible to properly provide a material fiber-reinforced composite, thus leading to the invention. That is, the invention is:
[0012] [012] a random mat characterized by the fact that the fiber reinforcement fiber areal weight with an average fiber length of 5 to 100 mm is 25 to 3000 g / m2, and consists of a bundle of reinforcement fibers (A) composed of multifibers equivalent to or more than the number of critical single fibers defined by formula (1), their ratio for the total amount of fibers in the mat is 30% by volume or less than 90% by volume , and the average number (N) of the fibers in the reinforcement fiber bundle (A) satisfies the following formula (2): critical single fiber number = 600 / D (1) 0.7 x 104 / D2 <N <1x105 / D2 (2) where D is the average fiber diameter (μm) of the single reinforcement fibers; a process for producing a random mat; and a reinforcement fiber composite material obtained. Effect of Invention Advantages
[0013] [013] The random mat of the invention is preferably usable as a preform for preparing a shaped fiber reinforced composite material, and a fiber reinforced composite material excellent in surface appearance quality may be provided. In addition, an excellent fiber reinforced composite material in reduced thickness and isotropy can be provided through the use of the random mat of the invention as a preform. The random mat of the invention, therefore, can be used as the preform for various constituent members, for example, inner plates, outer plates and constituent members of automobiles, various electrical appliances, structures and machinery boxes, and the like. Brief Description of Drawings
[0014] [014] Fig. 1 is a schematic view showing a step of cutting a bundle of fibers;
[0015] [015] Fig. 2 is an example (schematic, front and cross-sectional view) of a rotary spiral cutter.
[0016] [016] Fig. 3 is an example (schematic, front and cross-sectional view) of a rotary fiber separation cutter.
[0017] [017] Fig. 4 is an example (schematic, front and perspective views) of a cutter having blades parallel to a fiber direction. Best Mode for Carrying Out the Invention
[0018] [018] Exemplary modalities of the invention will in turn be described below. Random Treadmill
[0019] [019] The random mat of the invention includes reinforcement fibers having an average fiber length of 5 to 100 mm and a thermoplastic resin, the fiber fiber weight of the reinforcement fibers on the mat is 25 to 3000 g / m2, for a bundle of reinforcement fibers (A) composed of simple fibers equivalent to, or more than, the number of critical single fibers defined by formula (1), their ratio to the total amount of fibers in the mat is 30% by volume less than 90% by volume, and the average number (N) of the fibers in the reinforcement fiber bundle (A) satisfies the following formula (2): critical single fiber number = 600 / D (1) 0.7 x 104 / D2 <N <1x105 / D2 (2) where D is the average fiber diameter (μm) of the single reinforcement fibers.
[0020] [020] In a plane of the random mat, the reinforcement fibers are not oriented in a specific direction, and are dispersed and arranged in random directions.
[0021] [021] The random mat of the invention is an isotropic material in the plane. When a shaped product is obtained from the random belt, isotropy of the reinforcement fibers in the random belt is also maintained in the shaped product. Isotropy of the random conveyor and the product formed from it can be quantified by obtaining the conformed product from the random conveyor and determining the ratio of tension modules in two directions at right angles to each other. As the values of the voltage modules in two directions, when the ratio obtained by dividing a major by a minor does not exceed 2, it is assessed to be isotropic. When the ratio does not exceed 1.3, it is rated as being excellent in isotropy.
[0022] [022] The fiber beach weight of the reinforcement fibers in the random belt is within the range of 25 to 3000 g / m2. The random mat is useful as a prepreg, and various densities can be selected according to the desired impression. Reinforcement Fiber
[0023] [023] The reinforcement fibers making up the random mat are discontinuous, and contain reinforcement fibers having a certain fiber length range, so being able to develop a reinforcement function. The fiber length is expressed by the average fiber length determined by measuring the fiber length of the reinforcement fibers on the random mat obtained. Processes for measuring average fiber length include a process for measuring fiber length of 100 randomly extracted fibers, on the order of a millimeter, using a gauge or the like, and calculating their average.
[0024] [024] The average fiber length of the reinforcement fibers in the random mat of the invention is 5 to 100 mm, preferably 10 to 100 mm, more preferably 15 to 100 mm, and even more preferably 15 to 80 mm. In addition, it is preferably 20 to 60 mm.
[0025] [025] When the reinforcement fibers are cut to a certain length to produce the random belt by a preferred cutting process of the reinforcement fibers described later, the average fiber length of the fibers in the belt becomes approximately equivalent to the cutting length fiber.
[0026] [026] The reinforcement fibers composing the random mat are preferably at least one selected from the group consisting of carbon fibers, aramid fibers and glass fibers. These can be used together, and above all, however, carbon fibers are preferred in which a lightweight composite material with excellent strength can be provided. In the case of carbon fibers, the average fiber diameter is preferably 3 to 12 μm, and more preferably 5 to 7 μm.
[0027] [027] Like reinforcement fibers, those with a glue agent adhered to them are preferably used, and the glue agent is preferably more than 0 to 10 parts by weight based on 100 parts by weight of the reinforcement fibers. Fiber Opening Degree
[0028] [028] The random mat of the invention is characterized by the fact that it consists of a bundle of reinforcement fibers (A) comprising reinforcement fibers of at least the number of critical single fibers defined by formula (1), the bundle ratio of fibers for the total amount of fibers in the mat is 30% by volume to less than 90% by volume. Critical number of single fibers = 600 / D (1) where D is the average fiber diameter (μm) of the single reinforcement fibers. On the mat, single fibers or bundles of fibers each composed of single fibers of less than the critical number of single fibers are present as the reinforcement fibers other than the bundles of reinforcement fibers (A).
[0029] [029] That is, on the random track of the invention, the existing quantity of the bundles of reinforcement fibers (A) composed of single fibers equivalent to, or more than, the number of critical single fibers defined by formula (1), which is dependent of the average fiber diameter, it is adjusted to 30% in volume to less than 90% in volume. In other words, the fiber opening degree of the bundles of reinforcement fibers is controlled to contain the particular bundles of single fiber fibers equal to or more than the specific number of fibers and the open reinforcement fibers other than those in the specific one. reason. In order to adjust the existing quantity of the bundles of reinforcement fibers to 30% in volume or more and less than 90% in volume, control can be carried out, for example, with the blowing air pressure in a fiber opening step , or similar. In addition, control can also be performed by adjusting the size, for example, the width or the number of fibers per bundle width, of a bundle of fibers to be subjected to a cutting step. Specific examples include a process for extending the width of the fiber bundle by means of extension or the like, followed by subjection to the cutting step, and a process of providing a strip cutting step before the cutting step, and further includes a process of cutting fiber bundles through the use of a so-called fiber separating blade where many short blades are arranged, and a process of cutting into strips and simultaneously cutting the bundle of fibers. Preferred conditions will be described below in the section of the fiber opening step.
[0030] [030] In the case where the ratio of the bundles of reinforcement fibers (A) to the total amount of fibers is less than 30% by volume, it becomes difficult to obtain a fiber reinforced composite material excellent in mechanical physical properties when the the random mat of the invention is molded, although there is an advantage in that a composite material excellent in surface appearance quality is obtained. In the case where the ratio of the bundles of reinforcement fibers (A) is 90% by volume or more, portions of entangled fibers become locally thick, resulting in failure to obtain a thin-walled article. This defeats the purpose of the invention. The ratio of the fiber reinforcement bundles (A) is more preferably from 30% by volume to less than 80% by volume.
[0031] [031] In addition, the average number (N) of the single fibers in the bundles of reinforcement fibers (A) each comprising the fibers equivalent to, or more than, the critical number of single fibers satisfies the following formula (2): 0.7x104 / D2 <N <1105 / D2 (2) where D is the average fiber diameter (μm) of the single reinforcement fibers. Above all, the average number (N) of fibers in the bundles of reinforcement fibers (A) each composed of single fibers equal to, or more than, the critical number of single fibers is preferably less than 6x104 / D2. In order to adjust the average number (N) of fibers in the bundles of reinforcement fibers (A) to the range mentioned above, control can also be carried out to adjust the size, for example, the width of the bundle or the number of fibers per width of the fiber bundle, to be subjected to a cutting step, in a preferred production process described later. Specific examples include a process of widening the width of the fiber bundle by extending the fiber or the like, followed by subjection to the cutting step, and a process of providing a strip cutting step before the cutting step. In addition, the fiber bundle can be cut into strips at the same time as being cut.
[0032] [032] In addition, it is also possible to control the average number (N) of fibers in the bundles of reinforcement fibers (A) by adjusting the degree of opening of the bundle of cut fibers with the pressure of air blown in the opening step fiber, or the like. Preferred conditions will be described in the sections of the fiber opening step and the cutting step.
[0033] [033] Specifically, when the average diameter of carbon fibers composing the random mat is 5 to 7 μm, the critical number of single fibers is 86 to 120. When the average diameter of carbon fibers is 5 μm, the average number of fibers in the fiber bundles is within the range of more than 280 to less than 4000. Above all, it is preferably from 600 to 2500, and more preferably from 600 to 1600. When the average fiber diameter of the fibers of carbon is 7 μm, the average number of fibers in the fiber bundle is within the range of more than 142 to less than 2040. Above all, it is preferably from 300 to 1500, and more preferably from 300 to 800.
[0034] [034] When the average number (N) of fibers in the bundles of reinforcement fibers (A) is 0.7x104 / D2 or less, it becomes difficult to obtain a composite material having a high fiber volume content (Vf). In addition, when the average number (N) of fibers in the bundles of reinforcement fibers (A) is 1x105 / D2 or more, thicker portions can occur locally in composite materials, which are responsible for the cause of voids.
[0035] [035] When a composite material having a thickness of 1 mm or less is intended to be obtained, use of simply scattered fibers results in a large unevenness in fiber sand weight to fail to obtain good physical properties. Also, when all fibers are opened, it can become easy to obtain a finer one. However, fiber interlacing increases for failure to obtain one having a high fiber volume content. It becomes possible to obtain the random mat that is thin in thickness and excellent in physical properties obtained, through a random mat in which the bundles of reinforcement fibers (A) each composed of single fibers equal to, or more than, the number single fiber critic defined by formula (1) and reinforcement fibers (B) in a state of single simple fibers or bundle of finer fibers comprising single fibers of less than the critical number of single fibers that is present at the same time.
[0036] [036] It is possible to adjust the random mat of the invention to various thicknesses, and by using it as a preform, a thin-wall shaped product having a thickness of about 0.2 to 1 mm can also be appropriately obtained. That is, according to the invention, a random mat tailored to the thickness of various desired shaped products can be prepared, and is useful as a preform for a thin shaped product, particularly such as a surface layer of a sandwich material. . Thermoplastic Resin
[0037] [037] The random mat of the invention contains a solid thermoplastic resin, and becomes a preform for obtaining a fiber-reinforced composite material. In the random mat, the thermoplastic resin is preferably present in fibrous and / or particulate form. The reinforcing fibers and the thermoplastic resin in fibrous and / or particle form are present in a mixed state, making it unnecessary to allow the fibers and resin to flow into a mold, and the thermoplastic resin can be easily impregnated in the fiber bundles of reinforcement and spaces between single fibers of the reinforcement fibers at the moment of molding. The thermoplastic resin is preferably formed in fibrous and / or particulate form. Two or more types of thermoplastic resins can be used, and those fibrous and particulate resins can be used together.
[0038] [038] In the case of fibrous resin form, its fineness is preferably from 100 to 5000 dtex, and more preferably from 1000 to 2000 dtex. Its average length is preferably 0.5 to 50 mm, and more preferably 1 to 10 mm.
[0039] [039] In the case of particulate form, a spherical shape, a strip shape or a cylindrical shape such as a pellet is preferably exemplified. In the case of a spherical shape, a body of revolution of a perfect circle or an ellipse, or a shape such as an egg shape is preferably enumerated. In the case of spherical shape, the average particle size is preferably from 0.01 to 1000 μm, more preferably from 0.1 to 900 μm and even more preferably from 1 to 800 μm. Although there is no particular limitation on particle size distribution, fine distribution is more preferred for the purpose of obtaining a finer shaped product. However, a desired particle size distribution obtained by an operation such as classification can be used.
[0040] [040] In the case of a strip shape, a cylindrical shape such as a pellet, a prismatic shape or a plate shape is preferably enumerated, and a rectangular shape obtained by thin cutting a film is also preferred. In this case, a certain degree of aspect ratio may be allowed, but its preferred length must be considered to be in the same range as in the case of the fibrous shape mentioned above.
[0041] [041] Types of thermoplastic resins include, for example, a polyvinyl chloride resin, a polyvinyl chloride resin, a vinyl acetate resin, a polyvinyl alcohol resin, a polystyrene resin, a polyester resin acrylonitrile - styrene (AS resin), acrylonitrile - butadiene - styrene resins (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 resin 610, a polyacetal resin, a polycarbonate resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a resin polybutylene terephthalate, a polybutylene naphthalate resin, a polyarylate resin, a polyphenylene ether resin, a polyphenylene sulfide resin, a polysulfone resin, a poly ether sulfone resin, a polyether ether ketone resin, a poly lactic acid resin and the like. These thermoplastic resins can be used alone or in combination with a plurality of them.
[0042] [042] The amount of thermoplastic resin in the random mat is preferably 50 to 1000 parts by weight based on 100 parts by weight of the reinforcement fibers. It is more preferably from 55 to 500 parts by weight based on 100 parts by weight of the reinforcement fibers, and even more preferably from 60 to 300 parts by weight based on 100 parts by weight of the reinforcement fibers. Other Agents
[0043] [043] The random mat of the invention may contain additives such as various fibrous or non-fibrous fillers made from organic or inorganic fibers, a flame retardant, a UV resistant agent, a pigment, a release agent, an agent softener, a plasticizer, and a surfactant, within the range not harming the object of the invention. Production process
[0044] 1. A etapa de corte de feixes de fibras de reforço, 2. A etapa de introdução de feixes de fibras de reforço cortadas em um tubo, e abertura de feixe de fibras através de sopro de ar, 3. A etapa de aplicação de espalhamento e concorrentemente sucção das fibras reforçadas abertas, junto com uma resina termoplástica fibrosa ou em partículas, e espargimento de fibras de reforço e a resina termoplástica, e 4. A etapa de fixação de fibras de reforço e a resina termoplástica que foi aplicada. [044] A process for preferably obtaining the random mat of the invention will be described below. The random mat of the invention is preferably produced through the following steps 1 to 4. 1. The step of cutting bundles of reinforcement fibers, 2. The step of introducing bundles of reinforcement fibers cut into a tube, and opening the bundle of fibers by blowing air, 3. The application stage of spreading and concurrently suctioning the open reinforced fibers, together with a fibrous or particulate thermoplastic resin, and spreading of reinforcing fibers and the thermoplastic resin, and 4. The step of fixing reinforcement fibers and the thermoplastic resin that was applied.
[0045] [045] That is, the invention includes a process for producing a random conveyor including steps 1 to 4 mentioned above. The respective steps will be described in detail below. Cutting Stage
[0046] [046] A process for cutting reinforcement fibers in the process of the invention is specifically the step of cutting reinforcement fibers using a blade. As the blade used for cutting, a rotary cutter or the like is preferred. As the rotary cutter, one with a spiral blade or a so-called fiber separating blade is preferred in which many short blades are arranged. A specific schematic view of the cutting step is shown in Fig. 1. An example of the rotary cutter having the spiral blade is shown in Fig. 2, and an example of the rotary cutter having the fiber separating blade is shown in Fig. 3 .
[0047] [047] In order to adjust the average number (N) of fibers in the bundles of reinforcement fibers (A) to the preferred range of the invention, control is preferably carried out by adjusting the size of a bundle of fibers, for example, the bundle width or the number of fibers per width, to be subjected to the cutting step.
[0048] [048] As the fiber bundle provided for the cutting step, the bundle of reinforcement fibers previously having a number of fiber bundles within the range of formula (2) is preferably used. In general, however, the lower the number of fiber bundles, the more expensive the fiber price becomes. Thus when the bundle of reinforcement fibers having a high number of bundles of fibers, which is inexpensively available, is used, the bundle of fibers is preferably subjected to the cutting step after width adjustment or the number of fibers per width of the bundle of fibers to be subjected to the cutting step. Its specific examples include a process of finely spreading the bundle of fibers through an opening or the like to widen its width, followed by subjection to the cutting step, and a process of providing a step of cutting into strips of the fiber bundle before step cutting. In the case of the provision of a previous strip cutting step, the fiber bundle is submitted to the cutting step after the fiber bundle has been previously finalized for cutting. In this case, a common flat blade, a spiral blade or the like having no special mechanism can be used appropriately as the cutter.
[0049] [049] Still, his examples include a process for cutting fiber bundles using a fiber separator blade and a process for cutting fiber bundle strips while cutting it using a cutter having a strip forming function.
[0050] [050] In the case of using a fiber separating blade, the average number (N) of fibers can be decreased by using one having a narrow blade width, and conversely, the average number (N) of fibers can be reduced be increased by using one having a wide blade width.
[0051] [051] In addition, as the cutter having the function of forming strips, an example of a fiber separation cutter with blades having the function of cutting strips, which are parallel to a fiber direction, in addition to perpendicular blades to the fiber direction, it is shown in Fig. 4. In the cutter of Fig. 4, short blades perpendicular to the fiber direction are spirally provided at certain intervals, and at the same time being cut by them, the fibers can be cut by the parallel blades to the fiber direction.
[0052] [052] In the fiber separating blade as shown in Fig. 2, blades parallel to the fiber direction can also be provided between the fiber separating blades.
[0053] [053] In order to obtain the random mat for a reinforcing fiber thermoplastic resin, which is excellent in surface appearance quality, the unevenness in fiber fiber sand weight has a significant effect. According to a rotary cutter in which a common flat blade is arranged, the fibers are cut discontinuously. When the fibers are introduced as such in the application stage, the inequality occurs on the mat. In the same way, it is possible to produce a belt with a small inequality in fiber sand weight through continuous cutting of fibers without interruption through the use of a blade with a defined angle. That is, for the purpose of continuous cutting of the reinforcement fibers, the blade is preferably arranged on the rotary cutter regularly at a specific angle. The fibers are preferably cut in such a way that the angle between a circumferential direction and an arrangement direction of the blade satisfies the following formula (3): Blade pitch = width of a strip of reinforcement fibers x tg (90-θ) (3) where θ is the angle between the circumferential direction and the arrangement direction of the blade.
[0054] [054] The blades pitch in the circumferential direction is reflected as such in the fiber length of the reinforcement fibers.
[0055] [055] Figures 2 to 4 are examples of the blades in which the angle is defined as described above, and the angle θ between the circumferential direction and the direction of blade arrangement in these cutters is shown in the figures. Fiber Opening Stage
[0056] [056] The fiber opening step in the process of the invention is a step of opening a bundle of fibers by introducing cut reinforcement fibers into a tube and blowing air into the fibers. The degree of fiber gap, the amount of reinforcement fiber bundles (A) and the average number (N) of single fibers in the reinforcement fiber bundles (A) can be appropriately controlled by air pressure or the like. In the fiber opening step, the reinforcement fibers can be opened by direct air blowing into the fiber bundle at a wind speed of 1 to 1000 m / s, preferably through compressed air blowing holes. The wind speed is preferably from 5 to 500 m / s, and more preferably from more than 50 to 500 m / s. Specifically, holes having a diameter of about 1 to 2 mm are made at various locations in the tube through which the reinforcement fibers pass, and a pressure of 0.01 to 1.0 MPa, more preferably about 0.2 to 0.8 MPa, is applied from the outside to directly blow compressed air into the fiber bundle. The fiber bundle can remain longer by decreasing wind speed, and conversely, the fiber bundle can be opened to form a single fiber by increasing wind speed. Application Stage
[0057] [057] The application step in the process of the invention consists of suction steps of open reinforcement fibers, together with fibrous or particulate thermoplastic resin, while spreading them, and spreading the reinforcement fibers and resin thermoplastic at the same time. The open reinforcement fibers and the fibrous or particulate thermoplastic resin are applied on a sheet, specifically on a breathing sheet mounted on a lower portion of a fiber opening machine, preferably at the same time.
[0058] [058] In the application step, the amount of supply of the thermoplastic resin is preferably 50 to 1000 parts by weight based on 100 parts by weight of the reinforcement fibers. The thermoplastic resin is more preferably 55 to 500 parts by weight based on 100 parts by weight of the reinforcement fibers, and even more preferably 60 to 300 parts by weight based on 100 parts by weight of the reinforcement fibers.
[0059] [059] The reinforcing fibers and the fibrous or particular thermoplastic resin are preferably spread out so as to be here bidimensionally oriented. In order to apply the open fibers while orienting them in two dimensions, an application process and the following fixation process become important. In the process of applying the reinforcement fibers, it is preferred to use a tapered tube in a conical or similar way. In the tube of a circular cone or similar, air is diffused to decrease the flow rate in the tube, and at this moment, rotational force is given to the reinforcement fibers. The reinforcement fibers opened in the conical tube using this Venturi effect can preferably be spread and spread.
[0060] [060] Also, the following fixation step and the application step can be carried out at the same time, that is, the fibers can be fixed while being applied and deposited. It is preferred that the fibers are spread on a mobile aspirable sheet having a suction mechanism for depositing them in the form of a mat, followed by their fixation in that state. In this case, when the aspirable sheet is constituted by a conveyor comprising a network, and the fibers are deposited there while continuously moving it in one direction, the random mat can be continuously formed. In addition, the aspirable sheet can be moved back and forth and around, thereby obtaining uniform deposition. In addition, it is also preferred that a front edge of an application unit (spreading) of the reinforcement fibers and the thermoplastic resin is made reciprocal in a direction perpendicular to the direction of movement of the aspirable support moving continuously, and for that reason continuously performing the application and fixation.
[0061] [061] Reinforcement fibers and thermoplastic resin are preferably evenly spread without unevenness in the random mat. Fixation Step
[0062] [062] The fixation step in the process of the invention is a step of fixing applied reinforcement fibers and thermoplastic resin. Preferably, air is sucked from a lower portion of the aspirable sheet to fix the fibers. The thermoplastic resin spread along with the reinforcement fibers is also fixed while being mixed, through suction of air in the case of fibrous form or together with the reinforcement fibers even in the case of particulate form.
[0063] [063] The highly biaxially oriented mat can be obtained by suctioning from the lower portion through an aspirable sheet. In addition, the particulate or fibrous thermoplastic resin can be sucked using negative pressure generated, and in addition, easily mixed with the reinforcement fibers by diffusion flow generated in the tube. In the resulting reinforcement base material, the movement distance of the resin is short in an impregnation step through the presence of the thermoplastic resin in the vicinity of the reinforcement fibers, so that it is possible to impregnate the resin for a relatively short period of time. It is also possible to previously fix an aspirable or similar non-woven fabric made of the same material as the matrix resin to be used for a fixing part such as an aspirable sheet, followed by spreading reinforcement fibers and particles on the non-woven fabric. .
[0064] [064] Through the preferred production process mentioned above the random mat, there can be obtained the random fiber mat oriented two-dimensionally and containing few fibers whose long axes are three dimensionally oriented.
[0065] [065] The application step and the fixation step can be carried out at the same time. Also, when the random mat is produced industrially, application and fixing are preferably carried out at the same time while moving the aspirable sheet. Still, it is also preferred that the front edge of the application unit (spreading) of the reinforcement fibers and the thermoplastic resin are reciprocal in a direction perpendicular to the direction of movement of the aspirable support moving continuously, and for that reason, continuously applying and applying fixation. Fiber Reinforced Composite Material
[0066] [066] The random mat of the invention is molded as a preform, and therefore being able to obtain a fiber-reinforced composite material comprising the reinforcement fibers and the thermoplastic resin. As molding processes, press molding and / or thermoforming are preferred. The random mat of the invention is characterized by being easily impregnated with a thermoplastic resin, so that molding is carried out by hot pressing molding or the like to be able to efficiently obtain the fiber-reinforced composite material. Specifically, it is preferred that the thermoplastic resin on the random mat is melted under pressure and impregnated in the reinforcement fiber bundles and spaces between the single fibers of the reinforcement fibers, followed by cooling to perform molding.
[0067] [067] Thus, for example, the fiber-reinforced composite material similar to the board can be efficiently obtained for a short period of time. The board-like fiber-reinforced composite material is still useful as a prepreg for three-dimensional molding, particularly as a prepreg for press molding. Specifically, the molded product can be obtained through a so-called cold press where sheet of fiber-reinforced composite material similar to plate is heated to the melting point or higher, or to the glass transition temperature or higher of the resin, and one or a plurality of sheets are stacked according to the shape of the shaped product to be obtained are placed in a mold and kept at a temperature less than the melting point or less than the glass transition temperature of the resin, pressurized and then cooled.
[0068] [068] Alternatively, the shaped product can be obtained through a so-called hot press where the plate-like fiber-reinforced composite material is placed in a mold, press molding is carried out, while raising the temperature to the melting point or higher or to the glass transition temperature or higher, and then the mold is cooled to a temperature lower than the melting point or lower than the glass transition temperature.
[0069] [069] That is, the invention includes the fiber-reinforced composite material obtained from the random mat. As described above, in the random mat of the invention, the reinforcement fibers and the thermoplastic resin are mixed and present next to each other, so that the thermoplastic resin can be easily impregnated without having to allow the fibers and resin to flow into the mold. Also, in the fiber-reinforced composite material obtained from the random mat of the invention, it is possible to maintain the configuration of the reinforcement fibers, that is, isotropy. In addition, the degree of fiber opening of the reinforcement fibers in the random mat is also appropriately maintained in the fiber reinforced composite material.
[0070] [070] That is, the invention is preferably a composite material obtained from the random mat mentioned above, which is characterized by the fact that the composite material comprises reinforcing fibers having an average fiber length of more than 5 to 100 mm and a resin thermoplastic, the reinforcement fibers that are substantially randomly oriented two-dimensionally, that for bundles of reinforcement fibers (A) each composed of simple fibers equivalent to, or more than the critical number of simple fibers defined by formula (1), their The reason for the total fiber quantity is 30% by volume to less than 90% by volume, and the average number (N) of single fibers in the bundles of reinforcement fibers (A) satisfies the following formula (2): Critical number of single fibers = 600 / D (1) 0.7x104 / D2 <N <1x105 / D2 (2) where D is the average fiber diameter (μm) of the single reinforcement fibers.
[0071] [071] The average fiber length and fiber bundles of the reinforcement fibers in the composite material can be measured in the same way as in the random mat, after the resin is removed from the composite material. EXAMPLES
[0072] [072] Examples are shown below, but the invention should not be construed as being limited to them. 1) Bundle Analysis of Reinforcement Fibers on a Random Mat
[0073] [073] A random mat is cut to a size of about 100 mm x 100 mm.
[0074] [074] Fiber bundles are all taken with tweezers from the mat that has been cut, and the number of bundles (I) of the bundles of reinforcing fibers (A) and the length (Li) and weight (Wi) of the bundles of fibers are measured and annotated. For bundles of fibers that are small to such an extent that they cannot be taken with tweezers, their weight (Wk) is finally measured as a whole. For weight measurement, a scale that measures below 1/100 mg is used. From the fiber diameter (D) of the reinforcement fibers used in the random mat, the critical number of single fibers is calculated, and division in the bundles of reinforcement fibers (A) comprising single fibers equivalent to or more than the critical number of fibers. simple fibers and the others is carried out. Incidentally, in the case where two or more types of reinforcement fibers are used, splitting is performed for each type of fiber, and measurement and evaluation are performed for each one.
[0075] [075] A process for determining the average number (N) of fibers for the bundles of reinforcement fibers (A) is as follows. The number of fibers (Ni) in each bundle of reinforcement fibers is determined from the fineness (F) of the reinforcement fibers used, using the following formula: Ni = Wi / (LixF)
[0076] [076] The average number (N) of fibers in the bundles of reinforcement fibers (A) is determined from the number of bundles (I) of the bundles of reinforcement fiber (A) using the following formula: N = ΣΝi / I
[0077] [077] The ratio (VR) of the bundles of reinforcement fibers (A) to the total amount of fibers in the belt is determined using the fiber beach weight (ρ) of the reinforcement fibers using the following formula: VR = Σ (Wi / p) x100 / ((Wk + ΣWi) / p) 2) Average length analysis of fiber reinforcement fibers contained in a random mat or composite material
[0078] [078] The lengths of 100 fibers randomly extracted from a random mat or a composite material were measured up to a millimeter with a caliper and magnifying glass and noted. From the lengths (Li) of all measured reinforcement fibers, the average fiber length (La) was determined using the following formula. In the case of composite material, after a resin was removed in an oven at 500oC for about 1 hour, the reinforcement fibers were extracted. La = ΣLi / 100 3) Analysis of bundle of reinforcement fibers in composite material
[0079] [079] For a molded plate, for example, the reinforcement fiber composite material of the invention, after a thermoplastic resin is removed in an oven at 500oC for about 1 hour, measurement is performed in the same way as the process mentioned above in random mat. 4) Fiber Orientation Analysis in Composite Material
[0080] [080] As a process for measuring isotropy of fibers after the composite material is molded, a tensile test on the bases of any direction of the molded plate and a direction perpendicular to it was performed to measure the stress modules, and the stress modules. measured voltage, the ratio (Eδ) of a larger divided by a smaller was measured. The closer to 1 the ratio of the stress modules, the more excellent the isotropy is the material. In these examples, when the ratio of the modulus of elasticity is 1.3 or less, it is rated as being excellent in isotropy. Example 1
[0081] [081] As reinforcement fibers, carbon fiber yarns, "Tenax" (registered trademark) STS40-24KS (average fiber diameter: 7 μm, wire width: 10 mm), manufactured by Toho TENAX Co., Ltd, were used. ., and the wire has been enlarged in width to a width of 20 mm. As a cutting device, there was used a rotary cutter in which a spiral blade was laid on its surface, using a cemented carbide. At this time, θ in the following formula (3) was 63 degrees, and the blade pitch was adjusted to 10 mm in order to cut the reinforcement fibers to a fiber length of 10 mm. Blade pitch = width of a reinforcement fiber strip x tg (90-θ) (3) where θ is the angle between the circumferential direction and the blade.
[0082] [082] To prepare a fiber opening device, nipples made of SUS 304 different in diameter were welded to prepare a double tube and small holes were made in an inner tube. Compressed air was supplied between the inner tube and the outer tube using a compressor. At this time, the air wind speed from small holes was 450 m / s. This tube was placed just under the rotary cutter, and still, a tapered tube was welded to its lower portion. A matrix resin was supplied from the side of the tapered tube. As the matrix resin, particles obtained by spraying - frozen from pellets of a polycarbonate, "Panlite" (trademark L-1225L manufactured by Teijin Chemicals Ltd., followed by further classification by 20 mesh and 100 mesh, were used. mean particle of the polycarbonate spray was about 710 μm. Next, a movable table in XY directions was installed under an outlet of the tapered tube, and suction was performed from a lower portion of the table with a blower. the amount of supply of the reinforcement fibers was fixed to 180 g / minute, and the amount of supply of the resin matrix was fixed to 480 g / minute.The system was operated to obtain a random mat in which the reinforcement fibers and the resin thermoplastic fibers were mixed in. The configuration of the reinforcement fibers in the random mat was observed. As a result, fibers were randomly dispersed in the plane and the fiber axes approximately parallel to a plane. fiber average of the reinforcement fibers of the resulting random mat was 10 mm, and the amount of fiber fiber sand weight was 200 g / m2.
[0083] [083] For the resulting random mat, the ratio of the bundles of reinforcement fibers (A) and the average number (N) of fibers were examined. As a result, the critical number of single fibers defined by formula (1) was 86. For the bundles of reinforcement fibers (A), their ratio to the total amount of fibers in the mat was 35%, and the average number (N) of fibers in the bundles of reinforcement fiber (A) was 240. In addition, the pulverized polycarbonate was dispersed in the reinforcement fibers in a state with no great inequalities.
[0084] [084] The resulting random mat was heated in a press machine heated to 300oC, in 1 MPa for 3 minutes to obtain a molded plate (the fiber reinforced composite material of the invention, henceforth the molded plate) having a thickness of 0 , 6 mm. For the resulting molded plate, an ultrasonic inspection was carried out. As a result, an un-impregnated portion or a void was not observed.
[0085] [085] The voltage modules of the resulting plate molded in 0 degree and 90 degree directions were measured. As a result, the ratio (Εδ) of the stress modules was 1.03, and fiber orientation was scarcely observed. Thus, the material in which isotropy was kept can be obtained. In addition, this molded plate was heated in an oven at 500oC for about 1 hour to remove the resin, and the average fiber length of the reinforcement fibers was determined. As a result, it was 10 mm. The resin was removed from the molded plate, and the reinforcement fiber bundle ratio (A) and the average number (N) of fibers were examined. As a result, the ratio of the reinforcement fiber bundles (A) to the total amount of fibers was 35%, and the average number (N) of fibers in the reinforcement fiber bundles (A) was 240. Differences from of the measurement results mentioned above of the random treadmill were not observed. Example 2
[0086] [086] As reinforcement fibers, carbon fiber yarns, "Tenax" (trademark IMS60-12K (average fiber diameter: 5 μm, wire width: 6 mm) manufactured by Toho Tenax Co., Ltd. As a cutting device, a rotary cutter was used in which a spiral blade was laid on its surface, using a cemented carbide. Like this rotary cutter, there was used a fiber separation cutter in which blades parallel to a direction of fiber as shown in Fig. 4 were provided at 0.5 mm intervals, for the purpose of miniaturizing fiber bundles. At this point, θ in the formula (3) mentioned above was 17 degrees, and the blade pitch was adjusted to 20 mm The reinforcement fibers were cut to a fiber length of 20 mm. As a fiber opening device, a tube having small holes was prepared, and compressed air was supplied to it using a compressor. of air from the small holes was adjusted to 150 m / s. This tube was placed just under the rotary cutter, and still, a tapered tube was welded to its lower portion. A matrix resin was supplied from a lateral phase of the tapered tube. Like this matrix resin, PA 66 fibers (T5 Nylon manufactured by Asahi Kasei Fibers Corp., fineness: 1400 dtex) were used, which were cut dry to 2 mm. Then, a movable table in XY directions was installed under an outlet of the tapered tube, and suction was performed from a lower portion of the table with a blower. Then, the amount of supply of the reinforcement fibers was fixed to 1000 g / minute, and the amount of supply of the resin matrix was fixed to 3000 g / minute. The system was operated to obtain a random mat in which the reinforcement fibers and the thermoplastic resin were mixed. The configuration of the reinforcement fibers in the random mat was observed. As a result, the axes of the reinforcement fibers were approximately parallel to a plane, and ran-domestically dispersed in the plane. The average fiber length of the reinforcement fibers of the resulting random mat was 20 mm, and the amount of fiber fiber sand weight was 1000 g / m2.
[0087] [087] For the resulting random mat, the ratio of the bundles of reinforcement fibers (A) and the average number (N) of fibers were examined. As a result, the critical number of single fibers defined by formula (1) was 120. For the bundles of reinforcement fibers (A), their ratio to the total amount of fibers in the mat was 86%, and the average number (N) of fibers in the bundles of reinforcement fiber (A) was 900. Also, the nylon fibers were dispersed in the reinforcement fibers in a state with no great inequalities.
[0088] [088] The resulting random mat was heated in a press machine heated to 280oC, in 1 MPa for 3 minutes to obtain a molded plate having a thickness of 3.2 mm. For the resulting molded plate, an ultrasonic inspection was carried out. As a result, an un-impregnated portion or a void was not recognized.
[0089] [089] The voltage modules of the resulting plate molded in 0-degree and 90-degree directions were measured. As a result, the ratio (Εδ) of the modulus of elasticity was 1.07, and fiber orientation was scarcely observed. Thus, the material in which isotropy was kept can be obtained. In addition, this molded plate was heated in an oven at 500oC for about 1 hour to remove the resin, and the average fiber length of the reinforcement fibers was determined. As a result, it was 20 mm. The resin was removed from the molded plate, and the reinforcement fiber bundle ratio (A) and the average number (N) of fibers were examined. As a result, the ratio of the reinforcement fiber bundles (A) to the total amount of fibers was 86%, and the average number (N) of fibers in the reinforcement fiber bundles (A) was 900. Differences from of the measurement results mentioned above of the random treadmill were not observed. Example 3
[0090] [090] As reinforcement fibers, EX-2500 fiberglass yarns (average fiber diameter: 15 μm, wire width: 9 mm) manufactured by Nippon Electric Glass Co., Ltd. were used there. cutting, there was used a rotary cutter in which short blades in a 90 degree direction for the fibers were disposed obliquely and a fiber separating blade was laid out on its surface, using a cemented carbide. The blade width was 1 mm, and blades parallel to a fiber direction were provided between the blades, for the purpose of miniaturizing fiber bundles. At this time, θ in the formula (3) mentioned above was 10 degrees, and the blade pitch was adjusted to 50 mm. The reinforcing fibers were cut to a fiber length of 50 mm. As a fiber opening device, the same device used in Example 1 was used. The air wind speed from the small holes was adjusted to 350 m / s by decreasing the pressure of the compressor. This tube was placed just under the rotary cutter, and still, a tapered tube was welded to its lower portion. A matrix resin was supplied from a lateral phase of the tapered tube. Like this matrix resin, there was used a powder obtained by spraying - frozen from a polycarbonate, "Panlite" (registered trademark) L-1225L manufactured by Teijin Chemicals Ltd., followed by further classification through 30 mesh and 200 mesh. At this time, its average particle size was about 360 μm. Then, a movable table in XY directions was installed under an outlet of the tapered tube, and suction was performed from a lower portion of the table with a blower. Then, the amount of supply of the reinforcement fibers was fixed to 300 g / minute, and the amount of supply of the resin matrix was fixed to 600 g / minute. The system was operated to obtain a random mat in which the reinforcement fibers and the thermoplastic resin were mixed. The configuration of the reinforcement fibers in the random mat was observed. As a result, the axes of the reinforcement fibers were approximately parallel to a plane, and randomly dispersed in the plane. The average fiber length of the reinforcement fibers of the resulting random mat was 50 mm, and the amount of fiber fiber sand weight was 300 g / m2.
[0091] [091] For the resulting random mat, the ratio of the bundles of reinforcement fibers (A) and the average number (N) of fibers were examined. As a result, the critical number of single fibers defined by formula (1) was 40. For the bundles of reinforcement fibers (A), their ratio to the total amount of fibers in the mat was 68%, and the average number (N) of fibers in the bundles of reinforcement fiber (A) was 60. In addition, the polycarbonate powder was dispersed in the reinforcement fibers in a state with no major inequalities.
[0092] [092] The resulting random mat was heated in a press machine heated to 300oC, in 1 MPa for 3 minutes to obtain a molded plate having a thickness of 0.6 mm. For the resulting molded plate, an ultrasonic inspection was carried out. As a result, an un-impregnated portion or a void has not been confirmed.
[0093] [093] The voltage modules of the resulting plate molded in 0-degree and 90-degree directions were measured. As a result, the ratio (Εδ) of the modulus of elasticity was 1.14, and fiber orientation was scarcely observed. Thus, the material in which isotropy was kept can be obtained. In addition, this molded plate was heated in an oven at 500oC for about 1 hour to remove the resin, and the average fiber length of the reinforcement fibers was determined. As a result, it was 50 mm. The resin was removed from the molded plate, and the reinforcement fiber bundle ratio (A) and the average number (N) of fibers were examined. As a result, differences from the measurement results mentioned above from the random mat were not observed. Example 4
[0094] [094] As reinforcement fibers, carbon fiber yarns, "Tenax" (registered trademark) STS40-24KS (average fiber diameter: 7 μm, wire width: 10 mm), manufactured by Toho Tenax Co., Ltd ., which were opened to a fiber width of 30 mm. As a cutting device, a rotary cutter was used in which a spiral blade was laid out on its surface, using a cemented carbide. At this time, θ in the formula (3) mentioned above was 45 degrees, and the blade pitch was adjusted to 30 mm in order to cut the reinforcement fibers to a fiber length of 30 mm. To prepare a fiber opening device, nipples made of SUS 304 of different diameters were welded to prepare a double tube and small holes were made in an inner tube. Compressed air was supplied between the inner tube and an outer tube using a compressor. At this time, the air wind speed from small holes was 200 m / s. This tube was placed just under the rotary cutter, and still, a tapered tube was welded to its lower portion. A matrix resin was supplied from a lateral phase of the tapered tube. Like this matrix resin, there were used spray-frozen pellets of a polycarbonate, "Panlite" (registered trademark) L-1225L manufactured by Teijin Chemicals Ltd., followed by further classification through 20 mesh and 100 mesh. The average particle size of the polycarbonate spray was about 710 μm. Then, a movable table in XY directions was installed under an outlet of the tapered tube, and suction was performed from a lower portion of the table with a blower. Then, the amount of supply of the reinforcement fibers was fixed to 1000 g / minute, and the amount of supply of the resin matrix was fixed to 1100 g / minute. The system was operated to obtain a random mat in which the reinforcement fibers and the thermoplastic resin were mixed. The configuration of the reinforcement fibers in the random mat was observed. As a result, the axes of the reinforcement fibers were approximately parallel to a plane, and randomly dispersed in the plane. The average fiber length of the reinforcement fibers of the resulting random mat was 30 mm, and the amount of fiber fiber sand weight was 1000 g / m2.
[0095] [095] For the resulting random mat, the ratio of the bundles of reinforcement fibers (A) and the average number (N) of fibers were examined. As a result, the critical number of single fibers defined by formula (1) was 86. For the bundles of reinforcement fibers (A), their ratio to the total amount of fibers in the mat was 60%, and the average number (N) of fibers in the bundles of reinforcement fiber (A) was 1620. In addition, the polycarbonate powder was dispersed in the reinforcement fibers in a state with no major inequalities.
[0096] [096] Three layers of the resulting random mat were stacked, and heated in a press machine heated to 300oC, in 1 MPa for 3 minutes to obtain a molded plate having a thickness of 1.5 mm. For the resulting molded plate, an ultrasonic inspection was carried out. As a result, an un-impregnated portion or a void has not been confirmed.
[0097] [097] The voltage modules of the resulting plate molded in 0-degree and 90-degree directions were measured. As a result, the ratio (Εδ) of the elasticity modules was 1.01, and fiber orientation was scarcely observed. Thus, the material in which isotropy was kept can be obtained. In addition, this molded plate was heated in an oven at 500oC for about 1 hour to remove the resin, and the average fiber length of the reinforcement fibers was determined. As a result, it was 30 mm. The resin was removed from the molded plate, and the reinforcement fiber bundle ratio (A) and the average number (N) of fibers were examined. As a result, differences from the measurement results mentioned above from the random mat were not observed. Example 5
[0098] [098] As reinforcement fibers, carbon fiber yarns, "Tenax" (registered trademark STS40-24KS (average fiber diameter: 7 μm, wire width: 10 mm) manufactured by Toho Tenax Co., Ltd. , which were opened to a fiber width of 20 mm. As a cutting device, a rotary cutter was used in which a spiral blade was laid out on its surface, using a cemented carbide. At this moment, θ in formula (3) mentioned above was 68 degrees, and the pitch of the blades was adjusted to 8 mm in order to cut the reinforcement fibers to a fiber length of 8 mm. diameters were welded to prepare a double tube and small holes were made in an inner tube. Compressed air was supplied between the inner tube and an outer tube using a compressor. 350 m / s. This tube was disposed the one just under the rotary cutter, and yet, a tapered tube was welded to its lower portion. A matrix resin was supplied from a lateral phase of the tapered tube. Like this matrix resin, there were used spray-frozen pellets of a polycarbonate, "Panlite" (registered trademark) L-1225L manufactured by Teijin Chemicals Ltd., followed by further classification through 20 mesh and 100 mesh. The average particle size of the polycarbonate spray was about 710 μm. Then, a movable table in XY directions was installed under an outlet of the tapered tube, and suction was performed from a lower portion of the table with a blower. Then, the amount of supply of the reinforcement fibers was fixed to 1200 g / minute, and the amount of supply of the resin matrix was fixed to 1600 g / minute. The system was operated to obtain a random mat in which the reinforcement fibers and the thermoplastic resin were mixed. The configuration of the reinforcement fibers in the random mat was observed. As a result, the axes of the reinforcement fibers were approximately parallel to a plane, and randomly dispersed in the plane. The average fiber length of the reinforcement fibers of the resulting random mat was 8 mm, and the amount of fiber fiber sand weight was 1200 g / m2.
[0099] [099] For the resulting random mat, the ratio of the bundles of reinforcement fibers (A) and the average number (N) of fibers were examined. As a result, the critical number of single fibers defined by formula (1) was 86. For the bundles of reinforcement fibers (A), their ratio to the total amount of fibers in the mat was 38%, and the average number (N) of fibers in the reinforcement fiber bundles (A) was 220. In addition, the polycarbonate powder was dispersed in the reinforcement fibers in a state with no great inequalities.
[0100] [0100] Three layers of the resulting random mat were laminated, and heated in a press machine heated to 300oC, in 1 MPa for 3 minutes to obtain a molded plate having a thickness of 1.9 mm. For the resulting molded plate, an ultrasonic inspection was carried out. As a result, an un-impregnated portion or a void was not recognized.
[0101] [0101] The voltage modules of the resulting plate molded in 0-degree and 90-degree directions were measured. As a result, the ratio (Εδ) of the modulus of elasticity was 1.02, and fiber orientation was scarcely observed. Thus, the material in which isotropy was kept can be obtained. In addition, this molded plate was heated in an oven at 500oC for about 1 hour to remove the resin, and the average fiber length of the reinforcement fibers was determined. As a result, it was 8 mm. The resin was removed from the molded plate, and the reinforcement fiber bundle ratio (A) and the average number (N) of fibers were examined. As a result, differences from the measurement results mentioned above from the random mat were not observed. Example 6
[0102] [0102] Carbon fiber yarns, "Tenax" (registered trademark STS40-24KS (average fiber diameter: 7 μm, wire width: 10 mm, tensile strength of 4000 MPa), were used as reinforcement fibers. Toho Tenax Co., Ltd., which were enlarged in width to a fiber width of 30 mm. To cut the expanded wire, a cutter was used in which disc-like blades prepared using a cemented carbide were arranged at 1 mm intervals. As a cutting device, there was used a rotary cutter in which a spiral blade was placed on its surface, using a cemented carbide. At this point, θ in the formula (3) mentioned above was 45 degrees, and the pitch of the blades was adjusted to 30 mm in order to cut the reinforcement fibers to a fiber length of 30 mm. To prepare a fiber opening device, nipples manufactured from SUS 304 of different diameters were welded to prepare a double tube and small holes were made in a tub inside. Compressed air was supplied between the inner tube and an outer tube of the device using a compressor. At this time, the air wind speed from small holes was 350 m / s. This tube was placed just under the rotary cutter, and still, a tapered tube was welded to its lower portion. A matrix resin was supplied from a lateral phase of the tapered tube. Like this matrix resin, there were used spray-frozen pellets of a polycarbonate, "Panlite" (registered trademark) L-1225L manufactured by Teijin Chemicals Ltd., followed by further classification through 20 mesh and 100 mesh. The average particle size of the polycarbonate spray was about 710 μm. Then, a movable table in XY directions was installed under an outlet of the tapered tube, and suction was performed from a lower portion of the table with a blower. Then, the amount of supply of the reinforcement fibers was fixed to 500 g / minute, and the amount of supply of the resin matrix was fixed to 550 g / minute. The system was operated to obtain a random mat in which the reinforcement fibers and the thermoplastic resin were mixed. The configuration of the reinforcement fibers in the random mat was observed. As a result, the axes of the reinforcement fibers were approximately parallel to a plane, and randomly dispersed in the plane. The average fiber length of the reinforcement fibers of the resulting random mat was 30 mm, and the amount of fiber fiber sand weight was 500 g / m2.
[0103] [0103] For the resulting random mat, the ratio of the bundles of reinforcement fibers (A) and the average number (N) of fibers were examined. As a result, the critical number of single fibers defined by formula (1) was 86. For the bundles of reinforcement fibers (A), their ratio to the total amount of fibers in the mat was 35%, and the average number (N) of fibers in the reinforcement fiber bundles (A) was 270. In addition, the polycarbonate powder was dispersed in the reinforcement fibers in a state with no great inequalities.
[0104] [0104] Four layers of the resulting random mat were stacked, and heated in a press machine heated to 300oC, in 1 MPa for 3 minutes to obtain a molded plate having a thickness of 3.0 mm. For the resulting molded plate, an ultrasonic inspection was carried out. As a result, an un-impregnated portion or a void was not recognized.
[0105] [0105] The voltage modules of the resulting plate molded in 0-degree and 90-degree directions were measured. As a result, the ratio (Εδ) of the stress modules was 1.02, and fiber orientation was scarcely observed. Thus, the material in which isotropy was kept can be obtained. In addition, this molded plate was heated in an oven at 500oC for about 1 hour to remove the resin, and the average fiber length of the reinforcement fibers was determined. As a result, it was 30 mm. The resin was removed from the molded plate, and the reinforcement fiber bundle ratio (A) and the average number (N) of fibers were examined. As a result, differences from the measurement results mentioned above from the random mat were not observed. Example 7
[0106] [0106] As reinforcement fibers, carbon fiber yarns, "Tenax" (registered trademark STS40-24KS (average fiber diameter: 7 μm, wire width: 10 mm), manufactured by Toho Tenax Co., Ltd. were used. , which were enlarged in width to 30 mm. As a fiber separation device, a chisel was used in which disc-like blades prepared using a cemented carbide were arranged in 0.5 mm intervals. a rotary cutter was used in which a spiral blade made of cemented carbide was laid out on its surface, using a cemented carbide. At this point, θ in the formula (3) mentioned above was 45 degrees, and the blade pitch was adjusted to 30 mm in order to cut the reinforcement fibers to a fiber length of 30 mm.
[0107] [0107] A wire that passed through the cutter was introduced into a flexible conveyor tube disposed just under the rotary cutter, followed by its introduction into a fiber opening device. As a fiber opening device, a double tube prepared by welding nipples manufactured from SUS 304 of different diameters was used. Small holes were made in an inner tube, and compressed air was supplied between the inner tube and an outer tube using a compressor. At this time, the air wind speed from small holes was 100 m / s. A tapered tube increased in diameter downwards was welded to a lower portion of this tube.
[0108] [0108] From a side face of the tapered tube, a nylon resin, "A1030" manufactured by Unitika Ltd., was supplied as the matrix resin. Then, an aspirable support (hereinafter referred to as a fixing net) movable in a given direction was installed under an outlet of the tapered tube, and suction was performed from its lower portion with a blower. A mixture of the cut reinforcement fibers and the nylon resin was deposited in band form on that fixation net while alternating the flexible transport tube and the tapered tube in the wide direction. Then, the amount of supply of the matrix resin was fixed at 530 g / minute. The system was operated to obtain a random mat in which the reinforcement fibers and the thermoplastic resin were mixed on the support. The configuration of the reinforcement fibers in the random mat was observed. As a result, the axes of the reinforcement fibers were approximately parallel to a plane, and randomly dispersed in the plane. The average fiber length of the reinforcement fibers of the resulting random mat was 30 mm, and the fiber fiber sand weight was 500 g / m2.
[0109] [0109] For the resulting random mat, the ratio of the bundles of reinforcement fibers (A) and the average number (N) of fibers were examined. As a result, the critical number of single fibers defined by formula (1) was 86. For the bundles of reinforcement fibers (A), their ratio to the total amount of fibers in the mat was 85%, and the average number (N) of fibers in the reinforcement fiber bundles (A) was 370. In addition, the nylon powder was dispersed in the reinforcement fibers in a state with no great inequalities.
[0110] [0110] Two layers of the resulting random mat were stacked, and heated in a press machine heated to 260oC, in 1 MPa for 3 minutes to obtain a molded plate having a thickness of 1.5 mm. For the resulting molded plate, an ultrasonic inspection was carried out. As a result, an un-impregnated portion or a void has not been confirmed.
[0111] [0111] The voltage modules of the resulting plate molded in 0-degree and 90-degree directions were measured. As a result, the ratio (Εδ) of the modulus of elasticity was 1.03, and fiber orientation was scarcely observed. Thus, the material in which isotropy was kept can be obtained. In addition, this molded plate was heated in an oven at 500oC for about 1 hour to remove the resin, and the average fiber length of the reinforcement fibers was determined. As a result, it was 30 mm. The resin was removed from the molded plate, and the reinforcement fiber bundle ratio (A) and the average number (N) of fibers were examined. As a result, differences from the measurement results mentioned above from the random mat were not observed. Comparative Example 1
[0112] [0112] A random mat was prepared in the same way as in Example 1 with the exception that the air wind speed from the small holes was adjusted to 50 m / s. The configuration of the reinforcement fibers in the random mat was observed. As a result, the axes of the reinforcement fibers were approximately parallel to a plane, and randomly dispersed in the plane.
[0113] [0113] For the resulting random mat, the ratio of the bundles of reinforcement fibers (A) and the average number (N) of fibers were exhausted. As a result, the critical number of single fibers defined by formula (1) was 86. For the bundles of reinforcement fibers (A), their ratio to the total amount of fibers in the mat was 95%, and the average number (N) of fibers in the bundles of reinforcement fiber (A) was 1500.
[0114] [0114] The bundles of reinforcing fibers from the resulting random mat were thick, and a molded plate was prepared using this random mat in the same manner as in Example 1, and subjected to ultrasonic inspection. As a result, an un-impregnated portion was confirmed. In addition, the molded plate was cut and a cross section was observed. As a result, a portion not impregnated with the resin was confirmed within the fiber bundle. Comparative Example 2
[0115] [0115] A random mat obtained in the same way as in Comparative Example 1 was heated in a press machine heated to 300oC, at a high pressure to 4 MPa for 3 minutes to obtain a molded plate. The resulting molded plate was approximately doubled in area, and its thickness was reduced by approximately half to about 0.3 mm. In the resulting molded plate, a fiber flow can be visually confirmed. The voltage modules of the resulting molded plate in a flow direction and a 90 degree direction for the flow direction were measured. As a result, the ratio (Εδ) of the modulus of elasticity was 2.33, and it was confirmed that the fibers were highly oriented. In addition, this molded plate was heated in an oven at 500oC for about 1 hour to remove resin, and then the ratio of the bundles of reinforcement fibers (A) and the average number (N) of fibers were examined. As a result, differences in the measurement results of the random conveyor described in Comparative Example 1 were not observed. Description of Numerals and Reference Signs 1: fiber reinforcement 2: tightening roller 3: rubber roller 4: main body of a rotary cutter 5: blade 6: fiber reinforcement cut 7: blades pitch 8: blade parallel to a fiber direction

权利要求:
Claims (8)
[0001]
Random mat comprising: reinforcement fibers with an average fiber length of 5 to 100 mm; and a thermoplastic resin, where a fiber sands weight of the reinforcement fibers is 25 to 3,000 g / m2, characterized by the fact that the random mat consists of a bundle of carbon fibers (A) in a proportion of 30% by volume, to less than 90% by volume for a total amount of carbon fibers, the bundle of carbon fibers carbon (A) including carbon fibers of a critical single fiber number defined by formula (1) or more, and an average number (N) of the single carbon fibers in the carbon fiber bundle (A) meets the formula (2): critical number of single fibers = 600 / D (1) 0.7x104 / D2 <N <1x105 / D2 (2) where D is the average fiber diameter (μm) of the single reinforcement fibers.
[0002]
Random treadmill, according to claim 1, characterized by the fact that the amount of thermoplastic resin in the random mat is 50 to 1000 parts by weight based on 100 parts by weight of the reinforcement fibers.
[0003]
Random treadmill, according to claim 1, characterized by the fact that the thermoplastic resin is present in fibrous or particulate form.
[0004]
Random treadmill, according to claim 1, characterized by the fact that it has isotropy in the plane.
[0005]
Method for producing the random mat as defined in any one of claims 1 to 4, characterized by the fact that it comprises: cutting a bundle of carbon fibers; introduce the bundle of cut carbon fibers into a tube and open the bundle of carbon fibers by blowing air into the tube; spreading and simultaneously aspirating the open carbon fibers, together with a fibrous or particulate thermoplastic resin, and spraying the carbon fibers and the thermoplastic resin in a fixation portion; fix the cut carbon fibers and the thermoplastic resin that are sprayed to form a random mat.
[0006]
Carbon fiber reinforced composite material characterized by the fact that it is obtained by molding the random mat as defined in any one of claims 1 to 4.
[0007]
Carbon fiber reinforced composite material according to claim 6, characterized by the fact that the carbon fibers are randomly oriented bidimensionally.
[0008]
Carbon fiber reinforced composite material according to claim 6, characterized by the fact that a ratio obtained by dividing a higher value by a lower value of tensile modulus in two directions perpendicular to each other does not exceed 2.

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同族专利:

公开号 | 公开日

US8946342B2|2015-02-03|

KR101444631B1|2014-11-04|

ES2539902T3|2015-07-07|

KR20130141658A|2013-12-26|

CN103339308A|2013-10-02|

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RU2527703C1|2014-09-10|

JPWO2012105080A1|2014-07-03|

TW201233859A|2012-08-16|

EP2671991A4|2014-05-21|

US20130317161A1|2013-11-28|

TWI448596B|2014-08-11|

JP5436700B2|2014-03-05|

WO2012105080A1|2012-08-09|

EP2671991A1|2013-12-11|

BR112013019395A2|2020-10-27|

CN103339308B|2016-02-10|

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法律状态:
2020-11-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2020-11-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2021-02-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-04-06| 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:

申请号 | 申请日 | 专利标题

JP2011-019891|2011-02-01|

JP2011019891|2011-02-01|

PCT/JP2011/070314|WO2012105080A1|2011-02-01|2011-08-31|Random mat and fiber reinforced composite material|

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