random mat and shaped product made of fiber-reinforced composite material

专利摘要:
RANDOM CARPET AND PRODUCT CONFORMED OF FIBER-REINFORCED COMPOSITE MATERIAL. The present invention provides a fiber reinforced composite material which has isotropy and excellent mechanical strength and a random mat used as an intermediate material thereof. The random mat includes reinforcing fibers having an average fiber length of 3 to 100 mm and a thermoplastic resin, wherein the reinforcing fibers satisfy i) to iii). i) a weight average fiber width (Ww) of the reinforcing fibers satisfies the following Equation (1): 0.03 mm Ww 5.0 mm (1). ii) an average fiber width dispersion ratio (Ww/Wn) defined as a ratio of the weight average fiber width (Ww) to an average numerical fiber width (Wn) of the reinforcing fibers is from 1.8 to 20 ,0 inclusive. iii) a weight average fiber thickness of the reinforcing fibers is less than the weight average fiber width (Ww).
公开号:BR112014021249B1
申请号:R112014021249-0
申请日:2013-07-30
公开日:2021-05-25
发明作者:Naoaki Sonoda；Makoto Ootsubo；Takeru Ohki
申请人:Teijin Limited；
IPC主号:

专利说明:

FIELD OF TECHNIQUE
[001] The present invention relates to a random mat used as an intermediate material of a fiber reinforced composite material shaped product that includes a thermoplastic resin as a matrix and a fiber reinforced composite material shaped product obtained from same. TECHNICAL BACKGROUND
[002] As a fiber reinforced composite material in which a carbon fiber, an aramid fiber, a glass fiber or the like is used as a reinforcing fiber, an isotropic random mat was used due to formability or convenience of processing. Random matting can be obtained by a spray method (dry method) of simultaneously spraying a cut reinforcing fiber body or a thermoset resin into a mold, a paper making method (wet method) by adding a cut reinforcing fiber to a slurry containing a binder in advance or the like.
[003] As a means to improve the mechanical properties of a composite material, increasing a volume content ratio Vf of reinforcing fibers is known, but in the case of a random mat where cut fibers are used, it is difficult to increase the volume content ratio of reinforcing fibers due to the presence of three-dimensional direction fibers, many fiber tangles and the like. Furthermore, in the random mat use case, since the fibers are discontinuous compared to a continuous fiber use case, it is difficult to sufficiently develop the strength of the reinforcing fibers and a strength development ratio of the reinforcing fibers. after forming a shaped product it becomes 50% or less of a theoretical value. In Non-Patent Document 1, a composite material made from a random mat of carbon fiber in which a thermoset resin is used as a matrix is exemplified. The strength development ratio of the composite material is approximately 44% in relation to the theoretical value.
[004] In addition, a composite material in which a thermoplastic resin is used as a matrix in the related art was obtained by heating and pressurizing, using an autoclave for 2 hours or more, an intermediate material called a pre - impregnated, in which a thermoset resin is impregnated into a fiber-reinforcement base material in advance. Recently, an RTM method has been proposed in which a reinforcing fiber base material, in which a thermoset resin is not impregnated, is set in a mold and then the thermoset resin is molded into it. The RTM method concludes that a molding time is greatly reduced, but even in the case of using the RTM method, 10 minutes or more is required before a component is molded.
[005] Consequently, a composite in which thermoplastic resin is used instead of thermosetting resin as a matrix has gained attention.
[006] A TP-SMC thermoplastic stamping molding using a thermoplastic resin as a matrix (Patent Document 1) is a method in which cut fibers, in which the thermoplastic resin is impregnated in advance, are heated to a point of melting or more, in which the heated fibers are placed in a part of a mold, where the mold is immediately compressed and then the fibers and resin are allowed to flow into the mold to obtain a product shape and are cooled to mold a shaped product. In this method, the molding can be preformed in a short time of approximately 1 minute using the fibers in which the resin is impregnated in advance. The method is a method where you use a molding material called an SMC or a stampable sheet and, in thermoplastic stamping molding, there are problems in that, since the fibers and resin are allowed to flow into the mold, a Thin-walled product may not be produced and, since a fiber alignment is disorderly, its control is difficult.
[007] Furthermore, in Patent Document 2, the fibers in a fiber bundle are continuously distributed in a range of 1 mm to 15 mm fiber length, short fibers are aggregated while being randomly mixed to prevent the fibers from forming partially irregularity by aggregation and to obtain fiber assembly that is uniform and has excellent isotropy. However, in the method, there is a problem that the short fibers are also oriented in a thickness direction. QUOTE LIST PATENT DOCUMENT
[008] Patent Document 1: Japanese Patent No. 4161409
[009] Patent Document 2: Japanese Patent Application Opened to Public Inspection No. 5-9853 NON-PATENT DOCUMENT
[0010] Non-patent document1: Composites Part A 38 (2007) pages 755 to 770 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
[0011] However, in the related art, a shaped product of fiber reinforced composite material that has isotropy, excellent tensile strength and high tensile modulus is not studied. In order to solve many problems in the related art, an object of the present invention provides a shaped product of fiber reinforced composite material which has isotropy and excellent mechanical strength and a random mat used as an intermediate material thereof. Particularly, an object of the present invention provides a fiber reinforced composite material shaped product which has a high volume content ratio of the reinforcing fibers included in the fiber reinforced composite material shaped product and the fiber reinforced composite material shaped product has excellent traction module. SOLUTION TO THE PROBLEM
[0012] The inventors have revealed that to provide a shaped product of fiber-reinforced composite material that has excellent mechanical strength, excellent isotropy and high mechanical strength, particularly tensile modulus, from a random mat that includes a thermoplastic resin and reinforcing fibers which have a predetermined weight average fiber width, an average fiber width dispersion ratio, and a discontinuous weight average fiber thickness.
[0013] Furthermore, the inventors have revealed that in the random mat it is possible to prevent the occurrence of irregularity of partial aggregation of the reinforcement fibers by mixing reinforcement fibers that have different large and small sizes and in the random mat configured by only reinforcement fibers with a small diameter such as a single fiber shape, lining up in one direction of thickness and tangles of the fibers, it can prevent the mat from being bulky. Furthermore, by using the random mat which includes the reinforcing fibers having different large and small sizes, the inventors have found that to provide the fiber reinforced composite material shaped product having higher reinforcement fiber volume content ratio and more excellent mechanical strength completes the present invention.
[0014] That is, the present invention is a random mat that includes reinforcing fibers having an average fiber length of 3 to 100 mm and a thermoplastic resin, wherein the reinforcing fibers satisfy the following items i) to iii ) and a shaped product of fiber-reinforced composite material is obtained by molding them.
[0015] i) An average weight fiber width (Ww) of the reinforcing fibers satisfies the following Equation (1).0.03 mm < (Ww) < 5.0 mm (1)
[0016] ii) An average fiber width dispersion ratio (Ww/Wn) defined as a ratio between the weight average fiber width (Ww) and an average numerical fiber width (Wn) for the reinforcement fibers is 1 .8 or more and 20.0 or less.
[0017] iii) A weight average fiber thickness of the reinforcing fibers is less than the weight average fiber width (Ww). ADVANTAGEOUS EFFECTS OF THE INVENTION
[0018] According to the present invention, in the random mat including the thermoplastic resin and the reinforcing fibers, the included reinforcing fibers have a predetermined fiber width distribution to increase a filling property of the reinforcing fibers and have excellent mechanical strength. Also, in in-plane directions, the reinforcing fibers are not aligned in a predetermined direction, but are isotropic.
[0019] Consequently, since the fiber reinforced composite material shaped product obtained from the random mat of the present invention has excellent mechanical strength, excellent isotropy and high mechanical strength, particularly tensile modulus, the material shaped product fiber reinforced composite can be used in various types of constituent members, for example, an inner plate, an outer plate and constituent members of a vehicle, various types of electronics, a frame or casing of a machine or the like. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 is a schematic diagram of an example of a cutting process that uses a rotary cutter.
[0021] Figure 2 is a schematic diagram illustrating a front part and a cross section in an example of a preferred rotary separation counter.
[0022] Figure 3 is a schematic diagram of a preferred example of a method of opening and enlarging a fiber. DESCRIPTION OF MODALITIES
[0023] Hereinafter, the embodiments of the present invention will be described in sequence. In the disclosure of the present invention, a weight means a mass.
[0024] The present invention relates to a random mat that includes reinforcing fibers having an average fiber length of 3 to 100 mm and a thermoplastic resin, wherein the reinforcing fiber satisfies the following items i) to iii) .
[0025] i) A weight average fiber width (Ww) of the reinforcing fiber satisfies the following Equation (1).0.03 mm < Ww < 5.0 mm (1)
[0026] ii) An average fiber width dispersion ratio (Ww/Wn) defined as a ratio of the weight average fiber width Ww to an average numerical fiber width (Wn) for the reinforcing fiber is 1.8 or more and 20.0 or less.
[0027] iii) A weight average fiber thickness of the reinforcing fibers is less than the weight average fiber width (Ww).
[0028] The weight average fiber width (Ww) of the reinforcement fibers included in the random mat of the present invention can be obtained by the following Equation (5) from a width (hereinafter, also referred to as a fiber width or Wi) and a weight (hereinafter, also referred to as a fiber weight or wi) thereof and a total weight w of extracted reinforcement fibers, with respect to each of the reinforcement fibers having a sufficient number extracted from the random mat ( preferably from 200 to 1,000 drawn from the random mat of 100 mmx100 mm and more preferably from 300 to 1,000, eg 300).Ww = ∑(Wi x wi/w) (5)
[0029] In Equation (5), i is a natural number from 1 to the number of reinforcement fibers extracted from the random mat.
[0030] Regarding the random mat of the present invention, as shown in Equation (1), the weight average fiber width (Ww) of the reinforcement fibers is greater than 0.03 mm and less than 5.0 mm, preferably greater than 0.03 mm and less than 4.0 mm, preferably greater than 0.1 mm and less than 3.0 mm, that is, represented by the following Equation (2).0.1 mm < Ww < 3.0 m (2)
It is more preferably greater than 0.2 mm and less than 2.4 mm, and particularly preferably greater than 0.3 mm and less than 2.0 mm. When the weight average fiber width (Ww) of the reinforcing fibers is 0.03 mm or less, it can be difficult to control the dispersion ratio of the fiber width and when the weight average fiber width (Ww) of the reinforcement fibers is 5.0 mm or more, there are problems in that the filling property of the reinforcing fibers in the random mat may be impaired and the ratio of volume content of the reinforcing fibers or the mechanical strength of the shaped product obtained from the mat random may be insufficient.
[0032] In the random mat of the present invention, a median fiber width dispersion ratio (Ww/Wn) is defined as a ratio of the weight average fiber width (Ww) to an average numerical fiber width (Wn), for the reinforcement fibers included, is 1.8 or more and 20.0 or less and preferably 1.8 or more and 10.0 or less. The lower limit of (Ww/Wn) is preferably greater than 2.0, eg 2.01 or greater. A (Ww/Wn) is preferably greater than 2.0 and 15.0 or less, more preferably greater than 2.0 and 12.0 or less, most preferably greater than 2.0 and 10.0 or less, particularly preferably 2.0 and 8.0 or less and more preferably greater than 2.0 and 6.0 or less. It is preferred that the median fiber width dispersion ratio (Ww/Wn) (in the present invention, simply abbreviated as a dispersion ratio) is 1.8 or greater due to the fact that it is unreliable to form a gap between the fibers of reinforcement and the volume content ratio of reinforcement fibers is easily increased. It is not preferred that a (Ww/Wn) be greater than 20.0 due to the fact that it is difficult to control the scatter ratio.
[0033] Here, the average numerical fiber width (Wn) is calculated by the following Equation (4), after extracting a sufficient number (I) of reinforcement fibers from the random mat in the aforementioned order of the weight average fiber width (Ww) and measuring a Wi fiber width of each reinforcement fiber.Wn = ∑ Wi/I (4)
[0034] In the reinforcement fibers included in the random mat of the present invention, the weight average fiber thickness is less than the weight average fiber width (Ww) and the weight average fiber thickness is preferably 1/5 or less of the weight average fiber width (Ww), more preferably 1/7 or less, most preferably 1/10 or less, most preferably 1/20 and particularly preferably 1/50 or less. When the weight average fiber thickness of the reinforcement fibers is the same as the weight average fiber width (Ww), the fibers are oriented not only in a plane direction, but also in a thickness direction and, as a result, It is feared that a problem by the fact that it is difficult to increase the volume content ratio of reinforcing fibers due to tangling of the reinforcing fibers is caused.
[0035] In the present invention, reference is made to the short length as a "thickness" of lengths of two directions except for a longitudinal direction of the reinforcing fiber and the other length is referred to as a "width". When dimensions of two directions that are orthogonal to each other in a cross-section in the vertical direction to the longitudinal direction of the reinforcement fiber are the same as each other, reference is made to an arbitrary direction as a width of the reinforcement fiber and the other direction is Reference is made to a thickness of the reinforcing fiber.
[0036] The average weight fiber thickness of the reinforcement fibers included in the random mat of the present invention is preferably 0.01 mm or more and 0.30 mm or less, more preferably 0.02 mm or more and 0.20 mm or less, most preferably 0.03mm or more and 0.15mm or less, and particularly preferably 0.03mm or more and 0.10mm or less. In terms of impregnation of the thermoplastic resin which is to be a matrix, the weight average fiber thickness of the reinforcing fibers is preferably 0.30 mm or less. A value of 0.01 mm or more which is the lower limit of the weight average fiber thickness of the reinforcing fibers is not particularly strict.
[0037] However, the weight average fiber thickness t of the reinforcing fibers can be obtained by the following Equation (7) after operating the procedure as described in the weight average fiber width (Ww) and measuring a fiber thickness ti and a fiber weight wi of all extracted reinforcement fibers and a total weight w of the extracted reinforcement fibers. T = ∑(ti x wi/w) (7)
[0038] In a plan of the random mat of the present invention, the reinforcing fibers are not aligned in a specific direction, but arranged to be scattered in random directions. The random mat of the present invention is an in-plane isotropic intermediate material. In the shaped product obtained by processing the random mat of the present invention, the isotropic property of the reinforcing fibers in the random mat is maintained. The isotropic properties of the random mat and the shaped product from the random mat can be quantitatively evaluated by calculating a ratio of tensile moduli in two directions that are orthogonal to each other after obtaining the shaped product from the random mat. When a ratio obtained by dividing a larger value by a smaller value of tensile modulus values in both directions is not greater than 2 in the shaped product obtained from the random mat, it is considered as an isotropic property. When the ratio is not greater than 1.3, the isotropic property is considered to be excellent.
[0039] As described above, the random mat of the present invention is constituted by the reinforcing fibers having the specific weight average fiber width, the median fiber width dispersion ratio and the weight average fiber thickness and the thermoplastic resin. The random mat of the present invention preferably includes the thermoplastic resin and a reinforcing fiber mat comprised of the reinforcing fibers. The reinforcing fiber mat of the present invention is a flat (mat-like) body made of discontinuous reinforcing fibers without including a thermoplastic resin as a matrix. In the fiber reinforced mat according to the present invention, the reinforced fibers may include a sizing agent or a small amount of a binder in forming the mat. Furthermore, it is preferred that the reinforcing fibers are oriented in random directions in in-plan directions and the mat has substantially the same vertical and horizontal directions of property in in-plan directions.
[0040] The type of reinforcing fiber is not particularly limited and can be an individual or a combination of two or more types.
[0041] In the random mat of the present invention, as an embodiment in which the fiber reinforcement mat includes the thermoplastic resin, a thermoplastic resin of the powdered, fibrous or protruding type can be included in the fiber reinforcement mat, the thermoplastic resin as a matrix can retain the reinforcing fiber mat, or sheet or film type thermoplastic resin can be included in the reinforcing fiber mat or layered in the reinforcing fiber mat. The thermoplastic resin of the random mat can be in a molten state. Furthermore, it goes without saying that, when an average weight fiber width (Ww), a fiber width dispersion ratio (Ww/Wn) and the like, for the reinforcing fiber mat included in the random mat of the present invention are calculated, the calculated values can be considered as those of the random mat.
[0042] The random mat of the present invention can be used directly as a preform to obtain a shaped product of fiber reinforced material (hereinafter, simply referred to as a shaped product) that is a final shape. The random mat of the present invention can be used to obtain the shaped product which is the final shape after impregnation of the thermoplastic resin by heating or the like to form a prepreg. The random mat of the present invention includes the prepreg into which the thermoplastic resin is impregnated.
[0043] Here, the shaped product that is the final shape means a product shaped into a shape in which a product obtained by pressurizing and heating the random mat or a molded plate thereof is not further heated or pressurized (additionally molded) to to melt the thermoplastic resin as a matrix and to change a shape or a thickness of the obtained product.
[0044] Consequently, when the product obtained by pressurizing and heating the random mat or similar is cut to form another shape, polished to be thin and coated with a resin or similar to be thick, pressurization and heating are not preformed and, as a result, the product obtained is the shaped product which is the final form. Furthermore, the use of heating as a means of cutting or processing does not correspond to the heating described in this document.
[0045] Furthermore, in a case where the random mat to which a thermoplastic resin in a molten state is supplied is molded, when the supplied thermoplastic resin is molded in the molten state, for example, the shaped product can be obtained by molding that only includes pressurization.
[0046] The random mat of the present invention can be used to mold as is as a preform and can be used to mold after being formed as a molded board and can select various fiber area weights according to a desired molding. The fiber area weight of the reinforcing fibers in the random mat is preferably from 25 to 10,000 g/m2, more preferably from 50 to 4,000 g/m2, most preferably from 600 g/m2 to 3,000 g/m2 and most preferably from 600 g/m2 to 2,200 g/m2.
[0047] In the random mat of the present invention, a reinforced fiber width distribution (hereinafter, simply abbreviated as a fiber width distribution) represented by a graph or the like, wherein a fiber width of the included reinforcement fibers is a horizontal axis and a fiber weight fraction of the reinforcing fiber of each fiber width is a vertical axis, preferably has one or more peaks, and more preferably has at least two peaks. Here, the peak is not limited to a sharp shape and can be a mountain shape that has a wide medium width or a trapezoidal shape. Also, the peak can have a symmetrical shape or an asymmetrical shape.
[0048] When the reinforcement fiber width distribution of the reinforcement fibers included in the random mat of the present invention preferably has at least two peaks, the spaces between the reinforcement fibers in the random mat are additionally smaller and thus a property of padding can be improved.
[0049] When the width distribution of the reinforcing fiber has at least two peaks, the random mat can be obtained by using reinforced fibers tailored for at least two different types of distances.
[0050] As the at least two peaks of the fiber width distribution of the reinforcing fibers included in the random mat of the present invention, it is preferred that one peak is in a range of 0.01 mm or more and less than 0.50 mm of fiber width and the other peak is in a range of 0.50 mm or more and 2.00 mm or less of fiber width. Furthermore, it is preferred that one peak is in a range of 0.10 mm or more and less than 1.00 mm of the fiber width and the other peak is in a range of 1.00 mm or more and 5.00 mm or less than fiber width. Furthermore, the random mat having the peaks in the swaths and the fiber weight fraction of the fiber width in a small swath that is greater than the fiber weight fraction of the fiber width in a large swath is additionally preferred.
[0051] In the case where the fiber width distribution has three or more peaks, when two peaks of it fall within range, the remaining peak may be out of range or may be in range.[FIBER REINFORCEMENT]
[0052] The reinforcement fibers included in the random mat are discontinuous and characterized by the fact that they include a longer reinforcement fiber at a certain level to develop a reinforcement function. Fiber length is expressed as an average fiber length calculated by measuring the fiber length of the reinforcing fibers in the random mat obtained. The method of measuring the average fiber length may include a method of averaging by measuring a fiber length of 100 fibers that are randomly drawn in a 1 mm unit with a caliper or the like.
[0053] The average fiber length of the reinforcing fibers in the random mat of the present invention is 3mm or more and 100mm or less, preferably 4mm or more and 50mm or less, more preferably 5mm or more and 30mm or less and much more preferably 5 mm or more and 20 mm or less. In order to increase the filling property of reinforcing fibers in the random mat, the fiber length of the reinforcing fibers is preferably closer to the fiber width and a ratio of the average fiber length to the weight average fiber width (Ww ) is preferably 50/1 or less, more preferably 30/1 or less and most preferably 10/1 or less.
[0054] The fiber length distribution can be either a single type or a combination of two types or more.
[0055] In a preferred method of cutting reinforcement fibers to be described below, in the case of formation of a random mat by cutting the reinforcement fibers to a fixed length, the average fiber length becomes the same as the length of cut fiber.
[0056] The reinforcing fibers are preferably of at least one type selected from the group consisting of carbon fibers, aramid fibers and glass fibers. As the reinforcing fibers that make up the random mat, carbon fibers are preferred because carbon fibers can provide a lightweight composite material with excellent strength. As a carbon fiber, a polyacrylonitrile-based carbon fiber (hereinafter, abbreviated as PAN-based carbon fiber), a petroleum pitch-based carbon fiber, a coal-pitch-based carbon fiber, a rayon-based carbon fiber, a cellulose-based carbon fiber, a lignin-based carbon fiber, a phenol-based carbon fiber, a steam-based carbon fiber, and the like, not known in general and the present invention can suitably use any of these carbon fibers. Particularly, PAN-based carbon fiber is preferred and can be used either alone or in combination of a variety of types. The reinforcing fibers used in the random mat of the present invention may be carbon fibers alone or may include glass fibers or aramid fibers in order to impart impact strength. In the case of carbon fibers, an average fiber diameter is preferably 1 to 50 µm, more preferably 3 to 12 µm, most preferably 5 to 9 µm and most preferably 5 to 7 µm. It is preferred that carbon fibers with a sizing agent are used and the sizing agent can preferably be greater than 0 to 10 parts by weight based on 100 parts by weight of the carbon fibers.
[0057] The reinforcing fibers in the present invention may preferably be in an open state as a single strand, a fiber bundle having a plurality of individual filaments or in combination of the single strand and the fiber bundle. HEADQUARTERS]
[0058] Thermoplastic resin is a matrix resin included in the random mat of the present invention. The type of thermoplastic resin can include one or more types selected from the group consisting of, for example, a vinyl chloride resin, a vinylidene chloride resin, a vinyl acetate resin, a polyvinyl alcohol resin , a polystyrene resin, an acrylonitrile-styrene resin (AS resin), an acrylonitrile-butadiene-styene resin (ABS resin), an acrylic resin, a methacrylic resin, a polyethylene resin, a polypropylene resin, one 6 polyamide resin, one 11 polyamide resin, one 12 polyamide resin, one 46 polyamide resin, one 66 polyamide resin, one 610 polyamide resin, one polyacetal resin, one polycarbonate resin, one polyamide resin polyethylene terephthalate, a polyethylene naphthalate resin, a polybutylene naphthalate resin, a polybutylene terephthalate resin, a polyarylate resin, a polyphenylene ether resin, a polyphenylene sulfide resin, a resin of polysulfone, a polyethersulfone resin, a polyether-ether ketone resin, a polylactic acid resin, and the like. In the present invention, the thermoplastic resin can be used alone, in combination with a plurality of types or as a copolymer or a modified polymer.
[0059] The content of the matrix resin is preferably from 10 to 800 parts by weight, more preferably from 20 to 300 parts by weight, most preferably from 20 to 200 parts by weight, most preferably from 30 to 150 parts by weight and particularly preferably from 50 to 100 parts by weight, based on 100 parts by weight of the reinforcing fibres.
[0060] Furthermore, a ratio in quantity between the reinforcing fibers and the thermoplastic resin can be referred to by a ratio of volume content of reinforcing fibers (hereinafter, abbreviated as Vf) defined by the following Equation. of reinforcing fibers (% by volume) = 100 x [volume of reinforcing fibers/(volume of reinforcing fibers + volume of thermoplastic resin)]
[0061] The ratio of the volume content Vf of the reinforcement fibers and the thermoplastic resin content represented by parts by weight based on 100 parts by weight of the reinforcement fibers is converted using the density of the reinforcement fibers and the density of thermoplastic resin.
[0062] In addition, in the range without harming an objective of the present invention, additives such as various fibrous or non-fibrous fillers of organic fibers or inorganic fibers, flame retardants, anti-UV agents, pigments, release agents, softeners, agents, plasticizers and surfactants may be included in the random mat of the present invention.[PRODUCT FORMED OF FIBER-REINFORCED COMPOSITE MATERIAL]
[0063] Since the reinforcing fibers constituting the random mat have the above characteristics, the random mat of the present invention has an advantage of having high formality. Thus, the random mat of the present invention can be used as an intermediate material to obtain the fiber reinforced composite material shaped product.
[0064] That is, the present invention includes an invention of a shaped product of fiber reinforced composite material obtained from the random mat.
[0065] The fiber-reinforced composite material shaped product of the present invention includes reinforcing fibers having an average fiber length of 3 to 100 mm and a thermoplastic resin and it is preferred that the reinforcing fibers can satisfy the following items of i ) to iii).
[0066] i) A weight average fiber width (Ww) of the reinforcing fibers satisfies the following Equation (1). 0.03 mm < Ww < 5.0 mm (1)
[0067] ii) A dispersion ratio (Ww/Wn) defined as a ratio between the weight average fiber width (Ww) and an average numerical fiber width (Wn) for the reinforcing fiber is 1.8 or more and 20.0 or less.
[0068] iii) A weight average fiber thickness of the reinforcing fibers is less than the weight average fiber width (Ww).
[0069] The thickness of the fiber-reinforced composite material formed product of the present invention can be adjusted in a suitable range by controlling a fiber area weight and an amount of thermoplastic resin.
[0070] One type of reinforcing fibers constituting the fiber-reinforced composite material shaped product of the present invention is not particularly limited and may preferably include the examples described in the reinforcing fibers in the random mat.
[0071] A type of resin that constitutes the fiber reinforced composite material shaped product of the present invention is not particularly limited and may preferably include the examples described in the matrix resin in the random mat.
[0072] The thermoplastic resin content of the fiber reinforced composite material shaped product of the present invention is preferably from 10 to 800 parts by weight, more preferably from 20 to 300 parts by weight, most preferably from 20 to 200 parts by weight, most preferably from 30 to 150 parts by weight and particularly preferably from 50 to 100 parts by weight, based on 100 parts by weight of the reinforcing fibers, as described above based on the thermoplastic resin content in the mat. random.
[0073] A shape of the fiber reinforced composite material shaped product of the present invention is not particularly limited. The shape can be, for example, a sheet shape and a plate shape and it can have a curved portion and a cross section can be a shape that has a vertical plane such as a letter shape T, a letter shape L , a U-letter shape and a hat shape, and can be a 3D shape that includes these shapes.
[0074] The fiber-reinforced composite material shaped product of the present invention may have various types of thickness, for example, from 0.2 to 100 mm, but even if the fiber-reinforced composite material shaped product is a shaped product with thinner walls, a property or an appearance can be very good. In detail, the thickness of a molding plate can be from 0.2 mm to 2.0 mm (more precisely, a thickness at 25oC if extremely strict measurement is required). The fiber area weight of the reinforcing fibers in the fiber reinforced composite material shaped product is preferably from 25 to 10,000 g/m2, more preferably from 50 to 4,000 g/m2, more preferably from 600 g/m2 to 3,000 g/m m2 and most preferably from 600 g/m2 to 2,200 g/m2.
[0075] The present invention includes a laminate in which at least one type of fiber reinforced composite material shaped product of the present invention is used in a core or a skin layer. The laminate of the present invention may additionally include at least one type of unidirectional fiber reinforced composite material wherein continuous reinforcing fibers are unidirectionally arranged in parallel, such as the core or skin layer. The laminate of the present invention may additionally include at least one type of fiber reinforced composite material shaped product (hereinafter, referred to as another fiber reinforced composite material shaped product) in addition to the fiber reinforced composite material shaped product of the present invention or the unidirectional fiber reinforced composite material, such as the core or skin layer. The laminate of the present invention can additionally include at least one type of resin in which reinforcing fibers are not included, such as the core or skin layer.
[0076] The matrix resin of the unidirectional fiber-reinforced composite material or other shaped product of fiber-reinforced composite material and the resin in which reinforcing fibers are not included may be thermosetting resins or thermoplastic resins. random]
[0077] A method for manufacturing the random mat of the present invention is preferably a method that includes the following processes 1 to 4.
[0078] 1. A process for cutting the reinforcing fibers (cutting process)
[0079] 2. A process for introducing the cut reinforcement fibers into a tube, transporting the introduced reinforcement fiber by air and spraying them (spraying process)
[0080] 3. A process for fixing the sprayed reinforcing fibers to obtain a reinforcing fiber mat (fixing process)
[0081] 4. A process for adding a thermoplastic resin to the reinforcing fiber mat to obtain a random mat (thermoplastic resin addition process)<CUTTING PROCESS>
[0082] The process of cutting the reinforcing fibers will be described. As the reinforcing fibers to be cut, a shape in which individual long fiber fibers are grouped together, so called a filament, is easily obtained or handled to be preferred. The reinforcing fiber cutting method is a process of cutting the reinforcing fibers using a knife such as a rotary cutter. An example of the cutting process using the rotary cutter is illustrated in Figure 1. A knife angle to continuously cut the reinforcing fibers is not particularly limited and the knife can have a 90 degree blade or a certain angle relative to a blade. general fiber or a blade arranged in a spiral shape. An example of a rotary cutter that has a spiral knife is illustrated in Figure 2.
[0083] The random mat of the present invention is characterized by the fact that the reinforcing fibers have a specific fiber width distribution as described above. That is, spans between the reinforcing fibers are smaller by including fibers having different fiber widths in the random mat and thereby increasing the filling property. Fiber width distribution is not particularly limited and a peak shape thereof can be single or multiple.
[0084] In order to obtain a desired fiber width and a dispersion ratio of the reinforcement fibers, a size of the reinforcement fibers provided in the cutting process, such as a fiber width or a fiber thickness, can be controlled by the magnification method and a separation method to be described below. Furthermore, the cut reinforcement fibers are preferably opened by compressed air and the like to be thinner reinforcement fibers.
[0085] In addition, using a plurality of reinforcing fibers, an average fiber width or a random mat dispersion ratio can be controlled and in the cutting process or in the spraying process to be described below, the width of Average fiber or dispersion ratio can preferably be controlled by combining reinforcing fibers having different fiber widths or fiber thicknesses.
[0086] The fiber amplification method is not particularly limited and may include a method of pushing an expanded spreader such as a convex pin and the like into the fibers, a method of bending the fibers in a flow direction of a passing wind. if through an air flow in a direction transverse to a fiber processing direction, a method of applying vibration and the like. The enlarged reinforcement fibers can preferably have a desired fiber width using a fiber width control roller installed at a rear end.
[0087] Furthermore, in order to form the random mat of the present invention, the reinforcing fibers are enlarged as described above and then the width of the reinforcing fibers can be separated to be smaller (see Figure 3 as well).
[0088] The fiber separation method is not particularly limited and, for example, may include a method for using a chisel or the like so that a filament has fine bundles. In the case of filament separation using the chisel, a desired fiber width can be suitably obtained by controlling a cut gap. In addition, a chopper blade can preferably control a fiber width by passing fibers of a specific fiber width through a knife-type chopper blade to be separated or through a comb-type chopper blade to be selected. Furthermore, a desirable average fiber number of reinforcing fibers can be easily obtained by selecting a reinforcing fiber sizing agent and separating the reinforcing fibers.
[0089] As such, the reinforcing fibers can be controlled with a small fiber width or the like through fiber amplification and fiber separation. Therefore, it is possible to obtain the random mat whose expression of reinforcement function of the reinforcing fibers included in the random mat is excellent and the homogeneity is improved, irregularity in the thickness of the reinforcing fiber mat is small and mechanical strength is excellent. <SPRAYING PROCESS>
[0090] Subsequently, a spraying process is pre-formed by introducing the cut reinforcing fibers into a tapered tube on a downstream side of the cutter. A method of transporting the reinforcing fibers to the tapered tube is not particularly limited, but it is preferred to allow a suction wind velocity to be generated in the tapered tube and thus the reinforcing fiber can be transported to the tapered tube. through the air. During the cutting process, when a plurality of reinforcing fibers are cut separately, the reinforcing fibers can preferably be mixed in the tapered tube by mixing them in the tapered tube.
[0091] In addition, during the spraying process, compressed air is blown directly into the reinforcing fibers to properly widen the distribution of the reinforcing fiber widths. An area of the distribution can be controlled by the pressure of the blown compressed air.
[0092] The conveyed reinforcement fibers can preferably be sprayed on a permeable sheet installed below a spraying apparatus.
[0093] Furthermore, the transported reinforcement fibers can preferably be sprayed on a movable permeable sheet that has a suction mechanism, even for the following fixation process.
[0094] In addition, during the spraying process, a fibrous or powder-like thermoplastic resin is sprayed onto the sheet along with the reinforcing fiber cut at the same time to properly obtain the random mat that includes the reinforcing fibers and the resin thermoplastic. <FIXING PROCESS>
[0095] Subsequently, the sprayed reinforcing fibers are fixed to obtain the reinforcing fiber mat. In detail, the method for securing the reinforcing fibers sprayed by air suction from a lower portion of the permeable sheet to obtain the reinforcing fiber mat is preferred. Even in the case of spraying the reinforcing fibers and fibrous or powder-like thermoplastic resin at the same time, fibrous or powder-like thermoplastic resin is fixed to be accompanied by the reinforcing fibres. In addition, the fixing process can be continuously preformed with the spraying process of reinforcing fibers and the like during the spraying process.<THERMOPLASTIC RESIN ADDITION PROCESS>
[0096] The thermoplastic resin addition process can be simultaneously preformed with processes 1 to 3 above and, for example, during the spraying process as described above, the powder-type thermoplastic resin can be sprayed. When the reinforcing fiber mat is formed without adding thermoplastic resin during processes 1 to 3 above, the random mat of the present invention can be obtained by assembling or layering a sheet-like or film-like thermoplastic resin on the mat. reinforcing fiber and, in this case, the sheet-type or film-type thermoplastic resin may be in a molten state.
[0097] In addition, during the spraying process, in the random mat obtained by spraying the powder-type thermoplastic resin, the sheet-type, film-type or powder-type thermoplastic resin can be assembled or divided into layers as described above.[PREPARATION OF CONFORMED PRODUCT OF FIBER-REINFORCED COMPOSITE MATERIAL]
[0098] The random mat of the present invention can be molded to obtain the shaped product of fiber reinforced composite material. The method of obtaining the fiber reinforced composite material shaped product may include a method of obtaining the fiber reinforced composite material shaped product by heating and pressurizing the random mat obtained as described above using a press or the like. The method of obtaining the fiber reinforced composite material shaped product of the present invention is not particularly limited, but the shaped product can be suitably obtained by vacuum molding, hydraulic molding or hot press molding, a cold press or the like. The fiber reinforced composite material shaped product of the present invention may suitably be obtained by cold press molding in which the random mat is heated to a melting point or more or a glass transition temperature or more of the thermoplastic resin contained and inserted in molds whose temperatures are maintained at a melting point temperature or less or the glass transition temperature or less to obtain a shape.
[0099] In the case of molding the random mat, it is preferred that the random mat is heated to a melting point or more in the case where a thermoplastic resin that is a matrix is crystalline or at a temperature of a glass transition point or more in the case where the thermoplastic resin is amorphous. More preferably, the heated temperature is a temperature of one decomposition point or less of the thermoplastic resin. A pressurizing means can be controlled to the melting point or more or the glass transition point or more of the thermoplastic resin which is a matrix and controlled at the melting point or less or the glass transition point or less. Furthermore, during molding, thermoplastic resin can be suitably added to obtain the shaped product of fiber reinforced composite material which has a different thickness depending on a purpose. The thermoplastic resin to be added is not particularly defined and a detailed example might be the thermoplastic resin described in the matrix resin. In addition, one form of the resin may use a cast resin or a fibrous resin, either powder-like or film-like.
[00100] The random mat of the present invention can be used as is as a preform and can be formed as a molding plate to form a shaped product which is the final shape. [EXAMPLES]
[00101] Examples are illustrated below, but the present invention is not limited thereto. Particularly, unless mentioned, the units of fiber length, fiber width and fiber thickness of the reinforcing fibers or a sample thereof are in mm and a unit of weight is g. Additionally, the densities of the carbon fibers or thermoplastic resin used in the Examples and Comparative Example are as follows.
[00102] PAN-based carbon fiber "Tenax" (trademark) STS40-24K: 1.75 g/cm3
[00103] PAN-based carbon fiber "Tenax" (trademark) UMS40-24K: 1.79 g/cm3
[00104] PAN-based carbon fiber "Tenax" (trademark) HTS40-12K: 1.76 g/cm3
[00105] PAN-based carbon fiber "Tenax" (trademark) UTS50-24K: 1.79 g/cm3
[00106] Polypropylene: 0.91 g/cm3
[00107] Polyamide 6: 1.14 g/cm3
[00108] Polycarbonate: 1.20 g/cm3[METHOD TO CALCULATE AVERAGE NUMERIC FIBER WIDTH AND AVERAGE WEIGHT FIBER WIDTH OF REINFORCEMENT FIBER IN A RANDOM MAT]
[00109] The random mat is cut to 100 mm x 100 mm and 300 reinforcement fibers are extracted randomly with tweezers. A Wi fiber width, Wi fiber weight and Ti fiber thickness are measured and recorded for each of the extracted reinforcement fibers. A caliper that is measurable by 1/100 mm is used in a fiber width and fiber thickness measurement and a balance that is measured by 1/100 mg is used in a weight measurement. Small sized reinforcement fibers that are not measurable are collected to measure a fiber weight. Additionally, in the case of using two or more types of reinforcement fibers, the reinforcement fibers are divided into all types of reinforcement fibers and each of the reinforcement fibers is measured and evaluated.
[00110] With respect to all extracted fibers, Wi fiber width and Wi fiber weight are measured and then the average numerical fiber width (Wn) is calculated using Equation (4) below.Wn = ∑ Wi/I (4)
[00111] I is the number of reinforcing fibers and the fiber number is 300, except for a case of less than 300.
[00112] In addition, the weight average fiber width (Ww) of the reinforcement fibers is calculated by means of Equation (5) below the total weight w of the reinforcement fibers.Ww=∑(Wi x wi/w) ( 5)
[00113] Additionally, in the case where the reinforcing fibers and the thermoplastic resin are not separated from each other and thus the measurement is stopped after the thermoplastic resin is removed by heating to, for example, 500 °C per about 1 hour, the measurement is carried out.[METHOD TO CALCULATE LEAKAGE RATIO (WW/WN) IN REINFORCEMENT FIBERS]
[00114] The average fiber width dispersion ratio (Ww/Wn) is calculated by means of Equation (6) below from the calculated average numerical fiber width (Wn) and the calculated weight average fiber width (Ww) , of the reinforcement fibers obtained.
[00115] The Average Fiber Width Dispersion Ratio (Ww/Wn) = Weighted Average Fiber Width (Ww) / Average Numerical Fiber Width (Wn) (6)
[00116] [Method for checking a peak position of the reinforcement fiber width distribution in the random mat]
[00117] From the fiber width Wi and fiber weight wi calculated above and the total weight w of the reinforcing fibers, a graph of a fiber width and a fiber weight fraction (%) is prepared and displayed of a shape of the obtained reinforcement fiber width distribution, peak positions of the fiber width distribution are checked.
[00118] Additionally, in case of using two or more types of reinforcement fibers, a graph is prepared for each type of reinforcement fibers and each of the reinforcement fibers is evaluated.[METHOD TO CALCULATE AVERAGE WEIGHT FIBER THICKNESS OF FIBERS OF REINFORCEMENT ON THE RANDOM MAT]
[00119] In relation to all the extracted reinforcement fibers, after the fiber thickness ti and the fiber weight wi are measured, an average weight fiber thickness t is calculated by means of Equation (7) below.T = ∑ (ti x wi/w) (7)
[00120] [Method for calculating average numerical fiber width and weight average fiber width of reinforcing fibers in fiber reinforced composite material shaped product]
[00121] The average fiber width of the reinforcing fibers of the fiber reinforced composite material shaped product is calculated by extracting the fibers in the same order as the random mat to measure the fiber width Wi, the fiber weight wi and the like, after the composite shaped product is cut to 100mm x 100mm and the resin is removed by heating at 500°C for about 1 hour in a furnace. [METHOD TO CALCULATE MEDIUM FIBER LENGTH L IN REINFORCEMENT FIBER MAT OR RANDOM MAT]
[00122] 100 reinforcement fibers are randomly extracted from the reinforcement fiber mat or the random mat using a pair of tweezers and each length of Li fiber is measured by 1 mm using a caliper and recorded. Preferably the size during extraction can be in a large enough range in relation to the fiber length.
[00123] An average fiber length L is calculated from each fiber length Li obtained through the following Equation.L = ∑Li/100
[00124] Additionally, in the case where the reinforcing fibers and the thermoplastic resin are not separated from each other and thus the measurement is stopped after the thermoplastic resin is removed by heating at 500 °C for about 1 hour , the measurement is carried out.[DEGREE IMPREGNATION OF THERMOPLASTIC RESIN OF THE PRODUCT CONFORMED OF FIBER-REINFORCED COMPOSITE MATERIAL (MOLDING PLATE)]
[00125] The degree of impregnation of the formed product of fiber reinforced composite material (forming plate) is evaluated by an ultrasonic inspection. The degree of impregnation is assessed by carrying out the inspection at an inspection frequency of 5 MHz and a scan angle of 2.0 mm x 2.0 mm by an ultrasonic inspection imaging device (KJTD Co., Ltd, Ltd. SDS-WIN). In the evaluation, microscopic observation is performed on a partial cross-section that has a reflective wave strength of 90% or more and then verified that there is no defect or pore. On inspection, as an area ratio of a portion that has high reflective wave strength (70% or more in the exemplary modality) is large, the inside of the molding plate is dense, and the degree of impregnation of thermoplastic resin in the mold plate. molding is high. On the other hand, as the area ratio of a portion that has low reflective wave strength (50% or less in the exemplary embodiment) is large, tiny pore portions are present within the molding plate and there are many non-impregnated portions in the plate. of molding. [TRACTION TEST]
[00126] A specimen is cut from the shaped product of fiber-reinforced composite material (forming plate) using a water jet, and the tensile force and the tensile modulus are measured using a universal tester fabricated together to Instron Corporation with reference to JIS K 7164. A specimen shape is established as a Type B specimen based on 1B. A distance between pieces is 115 mm and a test speed is 10 mm/min. Additionally, the specimens are cut respectively in an arbitrary direction (0° direction) of the formed product and an orthogonal direction (90° direction ) for arbitrary direction and then tensile forces and tensile modulus in two directions are measured. Additionally, in relation to the traction modules, a ratio is calculated by dividing the value by a smaller value. [EXAMPLE 1]
[00127] As a reinforcing fiber, PAN-based carbon fibers "Tenax" (trademark), STS40-24K filament manufactured together with TOHO TENAX Co., Ltd. (Fiber diameter 7.0 µm, width of 10 mm fiber and 4,000 MPa tensile strength) have been expanded so that they have a width of 22 mm. Before the amplified fibers were processed by a separating apparatus, the amplified fibers were passed through a roller having an inner width of 20 mm and the fiber width was precisely controlled to have a width of 20 mm. The extended reinforcing fiber filament which is 20 mm wide was cut in a 1.2 mm interval at a line speed of 10 m/s and cut in a interval of 0.3 mm at a line speed of 30 m/s with the use of a magnetic disc-shaped separating blade made of cemented carbide to be fitted to two sets of cutting apparatus. The reinforcing fiber filament that was cut to two types of fiber widths was cut using a rotary cutter made of cemented carbide on which two blades were formed at a 12 mm interval as the cutting apparatus so that the fiber length was 12 mm. A tapered tube connected from the output side of the rotary cutter was arranged below the two rotary cutters. Compressed air was supplied to the tapered tube, each reinforcing fiber was introduced and transferred to the tapered tube at a suction wind speed of 5 m/s and two reinforcing fibers were mixed in the tapered tube. Polypropylene (J-106G, manufactured with Prime Polymer Co., Ltd.) ground and classified with a particle diameter of 500 µm, as a matrix resin, was provided from one side of the tapered tube. Next, although a movable carrier screen was installed below the outlet of the tapered tube to carry out suction by a fan below the screen, reinforcing fibers were provided from the tapered tube to obtain the random mat of an area weight of 1270 g/m2 fiber. When the shape of the reinforcing fibers in the random mat was observed, the geometric axes of the fibers of the reinforcing fibers were nearly parallel to a plane of the random mat and the reinforcing fibers were randomly dispersed in the plane.
[00128] An average fiber length of the obtained random mat reinforcing fibers was 12 mm and an average weight fiber thickness was 0.06 mm. The weight average fiber width (Ww) of the reinforcement fibers making up the random mat is 0.51 mm, the average numerical fiber width (Wn) was 0.25 mm and the dispersion ratio (Ww/ Wn) was 2.01. Additionally, fiber width and fiber weight fraction were represented by a graph and when peak positions of the fiber width distribution were checked, the peaks were checked at 0.29 mm and 1.18 mm of the fiber width .
[00129] The obtained random mat was heated to 4.0 MPa for 10 minutes by a pressure apparatus heated to 220 °C to obtain a molding plate having a thickness of 1.6 mm. When the ultrasonic inspection test was performed on the obtained casting plate, a portion where the force of the reflective wave was 70% or more was observed to be 80% or more.
[00130] The volume content ratio of the obtained molding board reinforcing fibers was 45% by volume, and as a result of evaluating a tensile characteristic based on JIS7164, the tensile strength was 490 MPa and the modulus of traction was 36 GPa. Additionally, a ratio in traction modulus of 0° and 90° steering was 1.04. [EXAMPLE 2]
[00131] As a reinforcing fiber, carbon fibers based on PAN “Tenax” (trademark), UMS40-24K filament manufactured in conjunction with TOHO TENAX Co., Ltd. (4.8 µm fiber diameter, width of 10 mm fiber and 4,600 MPa tensile strength) have been expanded so that they have a width of 16 mm. Before the amplified fibers were processed by a separating apparatus, the amplified fibers passed through a roller having an internal width of 15 mm and the fiber width was precisely controlled to have a width of 15 mm. The extended reinforcing fiber filament which is 15 mm wide was cut in a range of 0.8 mm at a line speed of 35 m/s and cut in a range of 0.2 mm at a line speed of 15 m/s with the use of a magnetic disc-shaped separating blade made of cemented carbide to be fitted to two sets of cutting apparatus. The reinforcing fibers were cut using a rotary cutter made of cemented carbide in which two blades were formed at an interval of 6 mm as the cutting apparatus so that the fiber length was 6 mm.
[00132] After the reinforcement fibers cut at an interval of 0.8 mm had been cut using a rotary cutter, the reinforcement fibers were introduced into the tapered tube at a suction wind speed of 5 m/s providing -compressed air to the tapered tube directly below the rotary cutter.
[00133] Reinforcement fibers cut at an interval of 0.2 mm were provided to the cutting apparatus and then transported to a tube that has a small hole of the sprinkler apparatus and compressed air was provided to the small hole with the use of a compressor to open the reinforcing fibers. In this case, the ejection speed of the small hole was 80 m/s. Thereafter, the open reinforcement fibers were introduced into the tapered tube and mixed with the cut reinforcement fibers at an interval of 0.8 mm in the tapered tube. Next, although a movable carrier screen was installed below the outlet of the tapered tube to carry out suction by a fan below the screen, reinforcing fibers were provided from the tapered tube to obtain the random mat of an area weight of fiber of 1,410 g/m2. When the shape of the reinforcing fibers in the fiber-reinforced random mat was observed, the fiber geometric axes of the reinforcing fibers were nearly parallel to a plane of the random mat, and the reinforcing fibers were randomly dispersed in the plane.
Subsequently, a molten matrix resin was provided in the mat. That is, as the matrix resin, polyamide 6 (A1030, manufactured together with Unitika Limited) was used and melted, a film-shaped melted resin body having a thickness of 1.2 mm was extruded from a T mold with a width of 1 m installed on a 5 cm upper side of the carrier network at the same speed as the line speed and the molten resin was provided to the entire mat. In that case, a portion where the resin was provided on the reinforcing fiber mat was heated by an infrared heater to prevent the resin from being cooled and solidified.
[00135] Furthermore, the apparatus was operated under a condition of a supply amount of the reinforcing fibers of 1410 g/min and a supply amount of the matrix resin of 1370 g/min and the random mat constituted by the reinforcing fibers and the thermoplastic resin was formed in the fixed network. Subsequently, the random mat on which the resin was uniformly impregnated by heating and pressurized by a pair of heating rollers at a set temperature of 280°C.
[00136] The average fiber length of the random mat reinforcement fibers obtained was 6 mm and the average weight fiber thickness was 0.07 mm. The weight average fiber width (Ww) of the reinforcement fibers making up the random mat was 0.52 mm, the average numerical fiber width (Wn) was 0.12 mm and the dispersion ratio (Ww/Wn) was 4.31. Additionally, fiber width and fiber weight fraction were represented by a graph and when peak positions of the fiber width distribution were checked, the peaks were checked at 0.08 mm and 0.79 mm of the fiber width. .
[00137] The obtained random mat was heated to 4.0 MPa for 10 minutes by a pressure apparatus heated to 260 °C to obtain a molding plate having a thickness of 2.0 mm. When the ultrasonic inspection test was performed on the obtained casting plate, a portion where the force of the reflective wave was 70% or more was observed to be 80% or more.
[00138] The volume content ratio of the obtained molding board reinforcing fibers was 40% by volume, and as a result of evaluating a tensile characteristic based on JIS7164, the tensile strength was 500 MPa and the modulus of tension was 51 GPa. Additionally, a ratio in tension modulus of 0° and 90° direction was 1.03. [EXAMPLE 3]
[00139] As a reinforcing fiber, PAN-based carbon fibers “Tenax” (trademark), HTS40-12K filament manufactured in conjunction with TOHO TENAX Co., Ltd. (Fiber diameter 7.0 μm, width of 8 mm fiber and 4,200 MPa tensile strength) have been expanded so that they have a width of 16 mm. Before the amplified reinforcement fibers were processed by a separating apparatus, the amplified fibers were passed through a roller having an internal width of 15 mm and the fiber width was precisely controlled to have a width of 15 mm. The extended reinforcing fiber filament which is 15 mm wide was cut in a range of 5.0 mm at a line speed of 20 m/s and cut in a range of 0.5 mm at a line speed of 20 m/s with the use of a magnetic disc-shaped separating blade made of cemented carbide to be fitted to two sets of cutting apparatus. The reinforcing fibers were cut using a rotary cutter made of cemented carbide on which blades were provided in a range of 30 mm as the cutting apparatus to have the fiber length of 30 mm. Reinforcement fibers having two types of fiber widths were cut by the rotary cutter, respectively. A tapered tube connected from an outlet side of the rotary cutter was arranged below the rotary cutter. Compressed air was supplied to the tapered tube, each reinforcing fiber was introduced and transferred to the tapered tube at a suction wind speed of 5 m/s and two reinforcing fibers were mixed in the tapered tube. As the matrix resin, from one side of the tapered tube, the polycarbonate (“Panlite” (trademark) L-1225 Y, manufactured with Teijin Chemicals Ltd.) is ground and classified with a particle diameter of 500 µm has been provided. Next, although a movable carrier screen was installed below the outlet of the tapered tube to carry out suction by a fan below the screen, reinforcing fibers were provided from the tapered tube to obtain the random mat of an area weight of 2,900 g/m2 fiber. When the shape of the reinforcing fibers in the random mat was observed, the geometric axes of the fibers of the reinforcing fibers were nearly parallel to a plane of the random mat and the reinforcing fibers were randomly dispersed in the plane.
[00140] The average fiber length of the random mat reinforcement fibers obtained was 30 mm and the average weight fiber thickness is 0.05 mm. The weight average fiber width (Ww) of the reinforcement fibers making up the random mat was 2.77 mm, the average numerical fiber width (Wn) is 0.73 mm and the dispersion ratio (Ww/Wn) was 3.82. Additionally, fiber width and fiber weight fraction were represented by a graph and when peak positions of the fiber width distribution were checked, the peaks were checked at 0.48 mm and 5.00 mm of the fiber width .
The obtained random mat was heated to 4.0 MPa for 10 minutes by a pressure apparatus heated to 300 °C to obtain a molding plate having a thickness of 3.0 mm. When the ultrasonic inspection test was performed on the obtained casting plate, a portion where the force of the reflective wave was 70% or more was observed to be 80% or more.
[00142] The volume content ratio of the obtained molding board reinforcing fibers was 55% by volume, and as a result of evaluating a tensile characteristic based on JIS7164, the tensile strength was 600 MPa and the modulus of traction was 44 GPa. Additionally, the ratio in traction modulus of 0° and 90° steering was 1.07. [COMPARATIVE EXAMPLE 1]
[00143] As a reinforcing fiber, PAN-based carbon fibers "Tenax" (trademark), HTS40-12K filament manufactured in conjunction with TOHO TENAX Co., Ltd. (Fiber diameter 7.0 µm, width of 8 mm fiber and 4,200 MPa tensile strength) have been expanded so that they have a width of 16 mm. Before the amplified reinforcement fiber was processed by a separating apparatus, the amplified fiber passed through a roller having an inner width of 15 mm and the fiber width was precisely controlled to have a width of 15 mm. The separating apparatus cut the reinforcing fiber filament into a 3.2 mm gap, using a magnetic disk-shaped separating blade made of cemented carbide. The cut reinforcing fiber filament was cut so that it has a fiber length of 30 mm with the use of a rotary cutter where blades were provided in a 30 mm range, as the cutting apparatus. The tapered tube was arranged directly below the rotary cutter. The cut reinforcing fibers were introduced and transferred to the tapered tube at a suction wind speed of 5 m/s and air was provided by compressing the tapered tube. As the matrix resin, from the tapered tube side, polycarbonate (“Panlite” (trademark) L-1225 Y, manufactured with Teijin Chemicals Ltd.) ground and classified with a particle diameter of 500 µm was provided . Next, although a movable carrier screen was installed below the outlet of the tapered tube to carry out suction by a fan below the screen, reinforcing fibers were provided from the tapered tube to obtain the random mat of an area weight of 2,900 g/m2 fiber. When the shape of the reinforcing fibers in the random mat was observed, the geometric axes of the fibers of the reinforcing fibers were nearly parallel to a plane of the random mat and the reinforcing fibers were randomly dispersed in the plane.
[00144] The average fiber length of the random mat reinforcement fibers obtained was 30 mm and the average weight fiber thickness was 0.05 mm. The weight average fiber width (Ww) of the reinforcement fibers making up the random mat was 3.04 mm, the average numerical fiber width (Wn) was 2.32 mm and the dispersion ratio (Ww/Wn) was 1.31. Additionally, fiber width and fiber weight fraction were plotted and when the peak positions of the fiber width distribution were checked, a single peak was found at 3.18 mm of the fiber width.
[00145] The obtained random mat was heated to 4.0 MPa for 10 minutes by a pressure apparatus heated to 300 °C to obtain a molding plate having a thickness of 3.2 mm. When the ultrasonic inspection test was performed on the obtained casting plate, a portion where the reflective wave strength was 70% or more was observed to be 58% or more and the portion without impregnation was checked on the casting plate.
[00146] The volume content ratio of the obtained molding board reinforcing fibers was 52% by volume, and as a result of evaluating a tensile characteristic based on JIS7164, the tensile strength was 440 MPa and the modulus of tension was 41 GPa. Additionally, the ratio in tension modulus of 0° and 90° direction was 1.16. [EXAMPLE 4]
[00147] As a reinforcing fiber, PAN-based carbon fibers “Tenax” (trademark), UTS50-24K filament manufactured in conjunction with TOHO TENAX Co., Ltd. (fiber diameter 6.9 µm, width of 10 mm fiber and 5,000 MPa tensile strength) have been expanded so that they have a width of 22 mm. Before the amplified reinforcement fibers were processed by a separating apparatus, the amplified fibers were passed through a roller having an internal width of 20 mm and the fiber width was precisely controlled to have a width of 20 mm. The extended reinforcing fiber filament which is 20 mm wide was cut in a range of 3.6 mm at a line speed of 35 m/s and cut in a range of 0.3 mm at a line speed of 15 m/s with the use of a magnetic disc-shaped separating blade made of cemented carbide to be fitted to two sets of cutting apparatus. The reinforcing fiber filament was cut using a rotary cutter made of cemented carbide where blades are provided at 20mm and 4mm intervals to have fiber lengths of 20mm and 4mm, like the cutting apparatus, respectively.
[00148] After the reinforcing fiber filament cut at a 3.6 mm interval was cut to 20 mm with the use of a rotary cutter, the reinforcing fibers were introduced into the tapered tube at a suction wind speed of 5 m/s by supplying compressed air to the tapered tube directly below the rotary cutter.
[00149] The reinforcing fiber filament cut at an interval of 0.3 mm was cut to 4 mm and then transported to a tube having a small hole of the sprinkler apparatus and compressed air was supplied to the small hole with use of a compressor to open the reinforcing fiber. In this case, the ejection speed of the small hole was 80 m/s. Thereafter, the reinforcement fibers cut at a 0.3 mm interval were introduced into the tapered tube and mixed with the reinforcement fibers cut at a 3.6 mm interval in the tapered tube. Additionally, as the matrix resin, from one side of the tapered tube, polyamide 6 ("A1030", manufactured together with Unitika Limited) ground and classified with a particle diameter of 500 µm was provided, a mobile carrier network was provided. installed below the outlet of the tapered tube and the carbon fibers were provided from the taper by carrying out suction by a fan below the mesh to obtain the random mat of a fiber area weight of 2900 g/m2. When the shape of the reinforcing fibers in the random mat was observed, the geometric axes of the fibers of the reinforcing fibers were nearly parallel to a plane of the random mat, and the reinforcing fibers were randomly dispersed in the plane.
[00150] The average fiber length of the random mat reinforcement fibers obtained was 15.2 mm and the average weight fiber thickness was 0.05 mm. The weight average fiber width (Ww) of the reinforcement fibers making up the random mat was 2.54 mm, the average numerical fiber width (Wn) was 0.38 mm and the dispersion ratio (Ww/Wn) was 6.68. Additionally, fiber width and fiber weight fraction were represented by a graph and when peak positions of the fiber width distribution were checked, the peaks were checked at 0.15 mm and 3.57 mm of the fiber width. . The obtained random mat was heated to 4.0 MPa for 10 minutes by a pressure apparatus heated to 260°C to obtain a molding plate having a thickness of 3.0 mm. When the ultrasonic inspection test was performed on the obtained casting plate, a portion where the force of the reflective wave was 70% or more was observed to be 80% or more.
[00151] The volume content ratio of the obtained molding board reinforcing fibers was 55% by volume, and as a result of evaluating a tensile characteristic based on JIS7164, the tensile strength was 620 MPa and the modulus of tension was 45 GPa. Additionally, the modulus ratio of 0° and 90° direction was 1.06. [EXAMPLE 5]
[00152] As a reinforcing fiber, PAN-based carbon fibers “Tenax” (trademark), STS40-24K filament manufactured together with TOHO TENAX Co., Ltd. (Fiber diameter 7.0 µm, width of 10 mm fiber and 4,000 MPa tensile strength) have been expanded so that they have a width of 20 mm. Before the amplified reinforcement fibers were processed by a separating apparatus, the amplified fibers passed through a roller having an internal width of 18 mm and the fiber width was precisely controlled to have a width of 18 mm. The extended reinforcing fiber filament which is 18 mm wide was cut in a range of 5.8 mm at a line speed of 30 m/s and cut in a range of 0.3 mm at a line speed of 20 m/s with the use of a magnetic disc-shaped separating blade made of cemented carbide to be fitted to two sets of cutting apparatus. The reinforcing fiber filament was cut using a rotary cutter made of cemented carbide in which two blades were provided in a 20 mm range as the cutting apparatus so that it has a fiber length of 20 mm.
[00153] After the reinforcing fiber cut at a 5.8 mm gap was cut using a rotary cutter, the reinforcing fibers were introduced into the tapered tube at a suction wind speed of 5 m/s providing -compressed air to the tapered tube directly below the rotary cutter.
[00154] The reinforcing fiber filament cut at an interval of 0.3 mm was cut and then transported to a tube having a small hole of the sprinkler apparatus and compressed air was supplied to the small hole with the use of a compressor to open the reinforcing fiber. In this case, the ejection speed of the small hole was 80 m/s. Thereafter, the open reinforcement fiber cut at an interval of 0.3 mm was introduced into the tapered tube and mixed with the reinforcement fibers cut at an interval of 5.8 mm in the tapered tube. Additionally, as the matrix resin, from the side of the tapered tube, polyamide 6 ("A1030", manufactured together with Unitika Limited) milled and classified with a particle diameter of 500 µm was provided, a mobile carrier network was installed. below the outlet of the tapered tube and the reinforcing fibers were provided from the tapered tube by carrying out suction by a fan below the screen to obtain the random mat of a fiber area weight of 2900 g/m2. When the shape of the reinforcing fibers in the random mat was observed, the geometric axes of the fibers of the reinforcing fibers were nearly parallel to a plane of the random mat and the reinforcing fibers were randomly dispersed in the plane.
[00155] The average fiber length of the random mat reinforcement fibers obtained was 20 mm and the average weight fiber thickness was 0.06 mm. The weight average fiber width (Ww) of the reinforcement fibers making up the random mat was 3.55 mm, the average numerical fiber width (Wn) was 0.37 mm and the dispersion ratio (Ww/Wn) was 9.69. Additionally, fiber width and fiber weight fraction were represented by a graph and when peak positions of the fiber width distribution were checked, the peaks were checked at 0.02 mm and 5.78 mm of the fiber width. . The obtained random mat was heated to 4.0 MPa for 10 minutes by a pressure apparatus heated to 260°C to obtain a molding plate having a thickness of 3.0 mm. When the ultrasonic inspection test was performed on the obtained casting plate, a portion where the force of the reflective wave was 70% or more was observed to be 80% or more.
[00156] The volume content ratio of the obtained molding board reinforcing fibers was 55% by volume, and as a result of evaluating a tensile characteristic based on JIS7164, the tensile strength was 500 MPa and the modulus of traction was 44 GPa. Additionally, the ratio in traction modulus of 0° and 90° steering was 1.12. [COMPARATIVE EXAMPLE 2]
[00157] As a reinforcing fiber, PAN-based carbon fibers "Tenax" (trademark), HTS40-12K filament manufactured in conjunction with TOHO TENAX Co., Ltd. (Fiber diameter 7.0 µm, width of 8 mm fiber and 4,200 MPa tensile strength) were cut using a rotary cutter so that they have a fiber length of 6 mm.
[00158] The chopped reinforcement fibers were provided to a dispersion tank and stirred for 3 minutes in 15 L water for the 9 g reinforcement fibers to be dispersed in a dispersion liquid. After being stirred for 3 minutes in the dispersion tank, the slurry of the obtained reinforcing fibers was fed to a 300 mm x 300 mm rectangular papermaking apparatus to obtain a papermaking base material having an area weight of reinforcing fiber 100 g/m2 removing the dispersed liquid. The obtained papermaking base material was heated and dried at a temperature of 100°C for 1 hour.
[00159] The weight average fiber thickness of the reinforcing fibers constituting the papermaking base material was 0.01 mm, the weight average fiber width (Ww) was 0.01 mm, the fiber width numerical mean (Wn) was 0.01 and the dispersion ratio (Ww/Wn) was 1.0, and the reinforcing fibers were completely dispersed so that they are a single fiber.
[00160] The papermaking base material and a polypropylene film (J-106 G, manufactured in conjunction with Prime Polymer Co., Ltd.) have been layered so that they have an area weight of fiber reinforcement ( carbon fiber) of 2600 g/m2 and the area weight of resin (polypropylene) of 1270 g/m2, and heated and pressurized by a pair of heating rollers to a temperature of 220 °C. Thereafter, the papermaking base material and the polypropylene film were heated to 10 MPa for 10 minutes by a pressure apparatus heated to 220°C to obtain an unimpregnated board having a thickness of about 30 mm. The board was released between layers because the resin was not sufficiently impregnated to assess the mechanical strength.
[00161] In the molding plate obtained, the average fiber length of the reinforcing fibers was 2.1 mm. That is, the average fiber length of the reinforcing fibers was reduced by about 1/3 of the average fiber length of the reinforcing fibers during cutting before the papermaking base material was prepared. This is because the reinforcing fiber was damaged during papermaking and pressure molding. [COMPARATIVE EXAMPLE 3]
[00162] As a reinforcing fiber, carbon fibers based on PAN “Tenax” (trademark) HTS40-12K filament manufactured in conjunction with TOHO TENAX Co., Ltd. (7.0 μm fiber diameter, fiber width 8 mm and a tractive force of 4,200 MPa) were used. Like the reinforcing fiber filament, the reinforcing fibers were cut in a range of 1.0 mm at a line speed of 35 m/s using a magnetic disk-shaped separating blade and were not cut but passed at a speed of 65 m/s to be provided to two sets of cutting apparatus, respectively. The reinforcing fibers were cut using a rotary cutter made of cemented carbide in which two blades were provided in a 30 mm interval as the cutting apparatus so that it had a fiber length of 30 mm.
[00163] The reinforcing fiber filament cut at an interval of 1.0 mm was cut by the rotary cutter and then transported to a tube having a small hole of the sprinkler apparatus and compressed air was provided to the small hole with use of a compressor to open the reinforcing fiber. In this case, the ejection speed of the small hole was 50 m/s.
[00164] The uncut reinforcement fibers were cut and then introduced to the tapered tube arranged directly below the cutter at a suction speed of 5 m/s. Thereafter, each reinforcing fiber was introduced to the tapered tube and two types of the reinforcing fibers were mixed in the tapered tube. Additionally, as the matrix resin, from the side of the tapered tube, the polycarbonate (“Panlite” (trademark) manufactured with Teijin Chemicals Ltd.) ground and classified with a 500 µm particle diameter was provided, a mesh mobile carrier was installed below the outlet of the tapered tube and the carbon fibers were provided from the taper by carrying out suction by a fan below the mesh to obtain the random mat of a fiber area weight of 2900 g/m2. When the shape of the reinforcing fibers in the random mat was observed, the geometric axes of the fibers of the reinforcing fibers were nearly parallel to a plane of the random mat and the reinforcing fibers were randomly dispersed in the plane.
[00165] The average fiber length of the random mat reinforcement fibers obtained was 30 mm and the average weight fiber thickness was 0.07 mm. The weight average fiber width (Ww) of the reinforcement fibers making up the random mat was 5.17 mm, the average numerical fiber width (Wn) was 1.94 mm and the dispersion ratio (Ww/Wn) was 2.67. Additionally, fiber width and fiber weight fraction were represented by a graph and when peak positions of the fiber width distribution were checked, the peaks were checked at 0.92 mm and 8.00 mm of the fiber width . The obtained random mat was heated to 4.0 MPa for 10 minutes by a pressure apparatus heated to 300°C to obtain a molding plate having a thickness of 3.2 mm. When the ultrasonic inspection test was performed on the obtained casting plate, a portion where the reflective wave strength was 70% or more was observed as 43% or more and many portions without impregnation were checked on the casting plate.
[00166] The volume content ratio of the obtained molding board reinforcing fibers was 51% by volume, and as a result of evaluating a tensile characteristic based on JIS7164, the tensile strength was 370 MPa and the modulus of traction was 32 GPa. Additionally, the modulus ratio of 0° and 90° steering was 1.23. INDUSTRIAL APPLICABILITY
[00167] Consequently, since the random mat and the fiber-reinforced composite material shaped product obtained from the present invention have excellent mechanical strength, excellent isotropy and high tensile modulus, the random mat and the shaped product of composite material reinforced by fibers can be used in various types of constituent members, for example, an inner plate, an outer plate and constituent members of a vehicle; and in addition to a structure, a housing, and so on, of various kinds of electrical products or a machine.
[00168] Although the present invention has been described with reference to detailed and specific embodiments thereof, it is obvious to those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the present invention.
[00169] This application is based on Patent Application No. JP 2012-171142, filed on August 1, 2012, the complete contents of which are incorporated herein by reference in its entirety. DESCRIPTION OF NUMERICAL REFERENCES Reinforcement fiberTractor roller 3:Rubber Roller Rotary Cutter Main BodyBlade

权利要求:
Claims (13)
[0001]
1. Random mat characterized by the fact that it comprises: reinforcing fibers (1) having an average fiber length of 3 to 100 mm; and a thermoplastic resin, wherein the reinforcing fibers (1) meet the following i) to iv):i) a weight average fiber width (Ww) of the reinforcing fibers (1) meets the following Equation (1):0, 03 mm < Ww < 5.0 mm (1); ii) an average fiber width dispersion ratio (Ww/Wn) defined as a ratio of the weight average fiber width (Ww) to an average numerical fiber width ( Wn) of the reinforcing fibers (1) is 1.8 or more and 20.0 or less; iii) an average weight fiber thickness of the reinforcing fibers (1) is less than the average weight fiber width (Ww ), and iv) the reinforcing fibers (1) are in an open state as an individual filament, a fiber bundle having a plurality of individual filaments, or in combination of the individual filament and the fiber bundle.
[0002]
2. Random mat according to claim 1, characterized in that the reinforcing fibers (1) are at least one type selected from the group consisting of a carbon fiber, an aramid fiber and a glass fiber.
[0003]
3. Random mat, according to claim 1 or 2, characterized in that the average weight fiber width (Ww) of the reinforcing fibers (1) satisfies the following Equation (2): 0.1 mm < Ww < 3.0 mm (2).
[0004]
4. Random mat according to any one of claims 1 to 3, characterized by the fact that a fiber width distribution of the reinforcing fibers (1) included in the random mat has at least two peaks.
[0005]
5. Random mat according to claim 4, characterized in that the fiber width distribution of the reinforcing fibers (1) included in the random mat has at least two peaks, one peak is in a range of 0.01 mm or more and less than 0.50 mm of fiber width, and another peak is in a range of 0.50 mm or more and 2.00 mm or less of fiber width.
[0006]
6. Random mat according to claim 4, characterized in that the fiber width distribution of the reinforcing fibers (1) included in the random mat has at least two peaks, one peak is in a range of 0.10 mm or more and less than 1.00 mm of fiber width, and another peak is in a range of 1.00 mm or more and 5.00 mm or less of fiber width.
[0007]
7. Random mat, according to any one of claims 1 to 6, characterized by the fact that the average fiber width dispersion ratio (Ww/Wn) of the reinforcing fibers (1) is more than 2, 0 and 10.0 or less.
[0008]
8. Random mat, according to any one of claims 1 to 7, characterized by the fact that the average weight fiber thickness of the reinforcing fibers (1) is 0.01 mm or more and 0.30 mm or less.
[0009]
9. Random mat, according to any one of claims 1 to 8, characterized by the fact that an area weight of fiber reinforcement is from 25 to 10,000 g/m2.
[0010]
10. Random mat according to any one of claims 1 to 9, characterized in that a content of the thermoplastic resin is 10 to 800 parts by weight based on 100 parts by weight of the reinforcing fibers ( 1).
[0011]
11. Product made of fiber-reinforced composite material characterized in that it is obtained from the random mat as defined in any one of claims 1 to 10.
[0012]
12. Product made of fiber-reinforced composite material, according to claim 11, characterized by the fact that a ratio obtained by dividing a larger value by a smaller value of tensile modulus values in two directions that are orthogonal to each other is less than or equal to 2.
[0013]
13. Product made of fiber-reinforced composite material, according to claim 11 or 12, characterized by the fact that a thickness is from 0.2 to 100 mm.

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/07/2013, 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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JP2012-171142|2012-08-01|

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JP2012171142|2012-08-01|

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PCT/JP2013/070603|WO2014021315A1|2012-08-01|2013-07-30|Random mat, and compact of fibre-reinforced composite material|

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